AU621638B2 - Creation of Inventions and Patents with Artificial Intelligence

AU621638B2 – Pyridinyl carbonyl cyclohexenone derivatives
– Google Patents

AU621638B2 – Pyridinyl carbonyl cyclohexenone derivatives
– Google Patents
Pyridinyl carbonyl cyclohexenone derivatives

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Publication number
AU621638B2

AU621638B2
AU38929/89A
AU3892989A
AU621638B2
AU 621638 B2
AU621638 B2
AU 621638B2
AU 38929/89 A
AU38929/89 A
AU 38929/89A
AU 3892989 A
AU3892989 A
AU 3892989A
AU 621638 B2
AU621638 B2
AU 621638B2
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AU
Australia
Prior art keywords
formula
hydrogen
alkyl
cyclohexanediones
cyano
Prior art date
1988-07-25
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AU3892989A
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Inventor
Hans-Georg Brunner
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Novartis AG

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Ciba Geigy AG
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1988-07-25
Filing date
1989-07-24
Publication date
1992-03-19

1989-07-24
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Ciba Geigy AG

1990-01-25
Publication of AU3892989A
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patent/AU3892989A/en

1992-03-19
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1992-03-19
Publication of AU621638B2
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patent/AU621638B2/en

2009-07-24
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members

C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members

C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom

C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

C07D213/62—Oxygen or sulfur atoms

C07D213/70—Sulfur atoms

A—HUMAN NECESSITIES

A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING

A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds

A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom

A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom

C07D213/46—Oxygen atoms

C07D213/50—Ketonic radicals

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/61—Halogen atoms or nitro radicals

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/62—Oxygen or sulfur atoms

C07D213/63—One oxygen atom

C07D213/65—One oxygen atom attached in position 3 or 5

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

C07D213/79—Acids; Esters

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

C07D213/79—Acids; Esters

C07D213/80—Acids; Esters in position 3

Description

Irrp rrrura~ I~Yr~ s~ s~~pl~innr~;maprr~-rur 621638 S F Ref: 101426 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete SpecificLtion Lodged: Accepted: Published: S Priority: Related Art: Name and Address of Applicant: o- Address for Servite: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle
SWITZERLAND
Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Nales, 2000, Australia Complete Specification for the invention entitled: carbonyl cyclohexenone derivatives”.
0 “Pyridinyl The following statement is a full description of this invention, including the best method of performing it known to me/us
J
1- 5-17144/1+2/+ “Pyridinyl carbonyl cyclohexenone derivatives’.
Abstract of the Disclosure The invention relates to novel herbicidally active cyclohexanediones of formula I or V’ oR R 3 4 0 CaChloloy or inGhaoll whic R’ and R independently of one aohraeec yrgn another are each hydrogen; CI-C 4 alkyl; or phenyl or benzyl each unsub- .4*stituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, Cl-C 4 alkyl, Cl-Ct~alkoxy, C1-Ciralkyl-S(O) Ci-Ct~haloalkyl, Ci-C~haloalkyl-S(O) n- and Cl-Ci~haloalkoxy; R6 is hydrogen; Cl-Cialkyl, Cl-Cialkoxycarbonyl; or cyano; R 7 is OH; or 0 H; R 8 is OH; C,-Ci~alkoxy; NH 2 Cl-04alkylamino; or di-Ci-Co 4 alkylamino; n is 0, 1 or 2; M+ is a cation equivalent of a metal ion or of an ammonium ion that is unsubstituted or substituted by up to three CI-Ci+alkyl, CI-Cz~hydroxyalkyl or C1-C~.alkoxy-CI-Ci~alkyl groups, to herbicidal compositions, to processes for the preparation of novel compounds and to novel intermediates and the preparation thereof.
1A- 5-17144/1+2/+ The present invention relates to novel cyclohexanediones having herbicidal activity, to agrochemical compositions containing those cyclohexanediones, to the use thereof for controlling undesired plant growth and to processes for the preparation of the compounds of the invention.
**to oo* The invention also relates to novel intermediates and to processes for the preparation thereof.
r Numerous substituted cyclohexane-1,3-diones having herbicidal activity are already known. These compounds are not always satisfactory in terms of strength of activity, duration of activity, selectivity and applicability. It has surprisingly been found that, in contrast to these known compounds, the novel cyclohexane-1,3-diones of the general formula I and I’ have good herbicidal activity.
o The invention relates to the novel cyclohexane-1,3-diones of formula I or I’
+-R
2 .O R3 N or R3 1 11 a 0* R 0 R R/ R 6 R5/ R6 in which R 1 and R 2 independently of one another are each hydrogen; halogen; nitro; cyano; Ci-C4alkyl; C1-C4alkoxy; C 1 -C4alkyl-S(O) COR C1-C4haloalkoxy; or C 1 -C4haloalkyl; R 3
R
4 and R 5 independently of one another are each hydrogen; CI-C4alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, Ci-C 4 alkyl, Ci-C4alkoxy, Cl-C4alkyl-S(0)n-, Cl-C4haloalkyl, Cl-C4haloalkyl-S(0) and C 1
-C
4 haloalkoxy;
R
6 is hydrogen; C1-C4alkyl; Cl-C4alkoxycarbonyl; or cyano; R 7 is OH; or -2
R
8 is OH; Ca-C4alkoxy; NH 2
C
1 -C~alkylamino; or di-Ci-C 4 ffl’,vlamino; n is 0, 1 or 2; M® is a cation equivalent of a metal oon or of an ammonium ion that is unsubstituted or substituted by up to three C 1
-C
4 alkyl, G 1 -Cshydroxyalkyl or C 1
-C
4 alkoxy-C 1 -Cialkyl groups.
In the definitions used in this description, the generic terms used, and the substituents obtainable by combining individual sub-terms, include, for example, the following specific individual substituents, but this list does not imply any limitation of the invention.
Alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and tert.-butyl; preferably methyl, ethyl and isopropyl.
Vr *1 Halogen: fluorine, chlorine, bromine and iodine; preferably fluorine, chlorine and bromine; especially preferably (for R 1 and fluorine and chlorine and bromine.
Haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 4 2-chloroetliyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl and dichlorofluoromethyl.
Alkoxy: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, iso-butoxy, sec.-butoxy and tert.–butoxy; preferably methoxy.
Haloalkoxy: fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-tri- ‘be.
:fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, 4-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl; preferably methoxycarbonyl and ethoxycarbonyl.
Alkylthio: methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec.-butylthio or tert.-butylthio; preferably methylthio and ethylthio.
3 Alkvlsulfinyl: methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, sec.-butylsulfinyl, isobutylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
Alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec.-butylsulfonyl, isobutylsulfonyl; preferably methyl- and ethyl-sulfonyl.
In view of their chemical structure, the compounds of formula I can be regarded as 1,3-cyclohexanediones acylated in the 2-position. Numerous tautomeric forms can be derived from this basic structure. The invention I includes all tautomers.
The individual meanings of the substituents R 1 to R 7 which are separated from each other by semi-colons, are to be regarded as sub-groups of those substituents. The invention includes also the definitions of compounds of formula I that can be obtained by deleting one or more of those subgroups.
t S The compounds of formula I and I’ exist in an equilibrium of the two er forms according to the following equation: II R3_ N a N R3_. R3′ S0 R R \R 7
R
5
\R
6
R
5
\R
6 I I’ In the case of the hydroxy compounds (R 7 OH), apart from the three enol forms Ia, and la’, the triketo form Ia” may occur in accordance with the following tautomeric equilibrium: r.
-4 Rl H 4k +-R 2 R3 T
“N
R’ 0 R 5/ \R6 Ia (la (R 7
OH)
iT t T-R2 Rx \N1 RI* \4 0 Rs/ \R6 Ia
RR
a/
)R
-4 N R3-
R
4 0
R
5
\R
6 Ia” X IT V
R
1 R2.
R
4
‘OH
R
5
/\R
6 Ia’ tee 4- f f~ I II 4- 4e~ t 4- 4 4- 4- 4-4- 4- 4- 4- 4-4- 4 4- The invention includes all the tautomeric structures that can be derived from the basic structures I and I’ and the salts thereof (R 7 OM Furthermore, the compounds of formula I and I’ may be asymmetrically ,substituted (especially by the radicals R 3 to R 6 in the c, lohexane system). The invention includes both the racemate and the enriched and optically pure forms of the respective stereoisomers.
The asymmetrically substituted compounds of formula I are generaliy Gee.
obtained in the form of racemates in the processes described in this o application, provided chiral educts are not used. The stereoisomers can thus be resolved according to methods that are known per se, such as, for example, by fractional crystallisation after salt formation with optically pure bases, acids or metal complexes, or by chromatographic processes on the basis of the physicochemical properties.
Both the racemate and the stereoisomeric forms are includd in the present invention.
Attention is drawn to the compounds of formula I or V’ 7 1 R 2 R’ 0 \R6 or
R-
1
N=/
R” R6 it in which the pyridinecarbonyl radical is bonded by way of the 2-position of th e pyridine system.
Attention is drawn also to the compounds of formula I or V’ I I ft St I It I I tI I I I If RR 2 R 0 or N Re 5/ R6 in which the radicals R’ and R 2 are the pyridine system.
bonded in the 3- and 5-positions of lIlt I I It I I II I I
II
I I t Ill Compounds of formula I or V’ 11t1 6444 4* 4 4 4 I ft.
N=-
R”
R3-iNr, R4 \R7 R’
R
in which the radicals R1 and R.
2 are bonded in the 3- and 5-positions of the pyridine ring and the pyridinecarbonyl system is bonded by way of the 2-position of the pyridine ring are preferred.
6- Especially preferred are the compounds of formula or V’ R’ 3-! R/ R/ \R7 R’ \R 99, 9 9, 9-9 0 99 0 90 0 09 4′ -99 9 o 0* 99 0 9 *0 1 9 00 09 ~0 o 0 0 in which RL is hydrogen; halogen; ritro; cyano; Ca-C~alkyl; C 1 -C4alkoxy;
C
1 -C4alkyl-S(O) COR 8 Cl-C4haloalkoxy; or Cl-C4haloalkyl; RI is hydrogen; halogen; nitro; cyano; C 1 -C~.alkyl; Ca-C~alkoxy; CI-C~haloalkoxy; CI-Ci 4 alkyl-S(O) or CI-Cz~haloalkyl; R 3, R 4 and RI independently of one another are each hydrogen; CI-Ci~alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, CI-Ct 4 alkyl, Cl-C4alkoxy, C1-Ckalkyl-S(O) n_1 C 1 -C4haloalkyl, Cl-C~haloalkyl-S(O) n- and CI-C 4 haloalkoxy; RI is hydrogen; CI-C~alkoxycarbonyl; or cyano; R 7 is OH; or 0 E)MG R8 is OH; CI-C~alkoxy; NH 2
C
1 -C4alkylamino; or di-Cl-C~alkylamino; n is 0, 1 or 2; His a cation equivalent of an alkali metal ion, an alkaline earth metal ion or an ammonium ion; of a mono-Ca–C4.-alkylammonium ion; of a di-Cl-C4g-alkylammonium ion; of a tri-Ca-Cz 4 alkylammonium ion; or of a tr-;ethanolammc-ium ion.
9000 0 09 #0 0. 90 o 0 0 9 09 Of the afore-mentioned compounds of formula I or V’ within the scope of the broadest generic meaning, and also of tbe emphasised, preferred and especially preferred generic definitions, attention is drawn in each case *4 especially to the sub-groups mentioned below: a) Compounds of formula I or 1′ in which at least one of the radicals R3 to R’ is hydrogen, b) Compounds of formula I or V’ in which at least two of the radicals R3 to RI exe hydrogen, c) Compounds of formula I or V’ in which R6 is cyano and R 5 is hydrogen, d) Compounds of formula I or V’ in which R6 is cyano, R5 is hydrogen and R3 and RI independently of one another are each hydrogen or Cl-C~alkyl, e) Compoundt, of formula I or V’ in which R6 is Cl-C4alkoxycarbonyl, f) Compounds of formula I or V’ in which R 7 is OH, g) Compounds of formula I or V’ in which R7 is 0 9-M 7 h) Compounds of formula I or I’ in which R 1 is hydrogen, chlorine, fluorine, nitro, trifluoromethyl, methoxy, bromine, methylthio, methylsulfonyl, carboxy, trichloromethyl or methyl, i) Compounds of formula I or I’ in which R 2 is hydrogen, chlorine, nitro, methylthio, methylsulfinyl, methylsulfonyl, methyl, fluorine, trifluoromethyl or trichloromethyl.
Attention is drawn especially to combinations of the sub-groups a) to e) with h) and i) both in the form of the free acid (group and in the form of salts (group Especially preferred are compounds of formula I or I’ in which R 1 is hydrogen; fluorine; chlorine; bromine; nitro; cyano; methyl; trifluoro- S methyl; trichloromethyl; methoxy; methylthio; methylsulfinyl; methylsulfonyl; carboxy; carbamoyl; methoxycarbonyl; or ethoxycarbonyl; R 2 is S hydrogen; fluorine; chlorine; nitro; trifluoromethyl; trichloromethyl; S methylthio; methylsulfinyl; or methylsulfonyl; R 3 is hydrogen; Ci-C 3 alkyl; phenyl; benzyl; or chlorophenyl; R 4 is hydrogen; or methyl; R 5 is hydrogen; or methyl; R 6 is hydrogen; cyano; methyl; or C1-C2alkoxycarbonyl; R 7 is OH; or 0 M M+ is a cation equivalent of a sodium, lithium, calcium, tricr.-thylammonium or triethanolammonium ion.
S The following may be mentioned as individual compounds: 2-(3-chloro-5- Stifluoromethylpyridin-2-ylcarbonyl)-cyclohex-l-en-l-ol-3-one and 2-(3-chloro-5-methylsulfonylpyridin-2-ylcarbonyl)-cyclohex-l-en-l-ol- 3-one.
S The compounds of formula Ia or Ia’ in which the radicals R 1 to R 6 are as defined hereinbefore and R 7 is OH can be prepared by a) reacting a cyclohexanedione of formula II, in which the radicals R 3 to
R
6 are as defined hereinbefore, with a pyridine of formula III, in which
R
1 and R 2 are as defined hereinbefore and X is halogen, preferably
R
I
chlorine or bromine or the radical O–OR or +-R 2 and R 8 is
N
C
1 -CLalkyl, phenyl or benzyl, in the presence of a base 8 R 4 0
R
s 5 \R 6
+-R
2
N
R
1 base
\N
-HX R3- R4 R \R6 Ia (R 7
OH)
R3_ Ra (R R R 5/R Ia (R 7
OH)
Ii rrr o C 48 00OI 0 848 8488 8 8088 b) thermal rearrangement of an ester of formula radicals R 1 to R 6 are as defined hereinbefore
R
1
-R
2 N
R
3
R/
R
3
R
4 0
R
R
5
\R
6
A
IV
r/ or/ IV or IV’ in which the
\R
6 Ia (R 7
OH)
or
R
1 C__R2 i\i \N
\R
7
\R
6 R1 R4 0- +-R 2
R
R3 B
R
4
R
5 IV’ Ia’ (R 7
OH)
preferably in the presence of cyanide.
The salts of formula Ib and Ib’ in which the radicals R’ to R 6 are as defined hereinbefore and R 7 is 0 M can be prepared by r, I r.
I
4 11
I
:1
I
I
I
I
I
I.1 11
I
I
-9 c) reacting a cyclohexanedione la or la’ in which R 1 to R 6 are as defined hereinbefore and R 7 is OH with a base V in which B is OH M M® being as defined hereinbefore Rr
M
R
R3-! R \R6 Ia (R 7
OH)
V1 B t1 t r or I I; vt S r r t S S t T
R
1 +-R2
N
R5 R6 Ib (R 7 0M®) R3 R \R 7 Ib’ (R 7 0M) R 4 \R 7 R’ (R O) Ia’ (R 7
OH)
The esters of formula IV and IV’ are valuable intermediates for the 9 preparation of the herbicidal end products Ia and Ia’ respectively T according to process variant The invention thus also relates to the novel esters IV and IV’. The esters IV and IV’ can, however, also be formed as by-products in the acylation according to process variant a).
d) Furthermore, the compounds of formula Ic or Ic’ in which one or more of the radicals R 1 to R 6 is (are) Cl-C4alkyl-S(O) n representing a* n 1 or 2, and the remaining radicals are as defined hereinbefore, can be prepared by oxidising a thioether of formula Id or Id’, wherein the radical from the group R 1 to R1 that is to be oxidised is C 1 -C4alkyl-S(O) with n representing 0, and the remaining radicals are as defined hereinbefore.
r 10
RI
7 S +-R 2 R 3 N R4 0
R
s 5
\R
6 Id (thioether, n representing 0)
RI
R3-!
R
5 \R6 Id’ (thioether n representing 0)
R
I
4 R3- N1
R
4 0
R
5
\R
6 oxidation ft *t r v c I f Ic (sulfinyl or sulfonyl compound, n representing 1 or 2)
RI,
R 4
R
R3_: R \R6 Ic’ (sulfinyl or sulfonyl compoud, n representing 1 or 2) *044 o rr 9 *0l 9 *4 a oat 4’I 0R a a.r 9 Such oxidations are familiar to the person skilled in the art (for example Methodicum Chimicum., Ed. F. Korte, 9. Thieme Verlag Stuttgart 1976, vol. 7, pages 696-698 and the literature sources mentioned there for oxidation to sulfenes, and vol. 7, pages 751-755 and the literature mentioned there for oxidation to sulfones).
Oxidation with H 2 0 2 and with per acids, especially with 3-chloroperbenzoic acid, is preferred.
By appropriate selection of bases, solvents and other reaction parameters, such as temperature, concentration etc., the 0-acylation may become the main reaction in accordance with the following scheme: 11
R
1 I I +-R 2 I I R R3
R
4 N R 4 Rs \R 6
R
5
\R
6 II III IV and/or
R
R SR/
/O-R
Ri 0I 2Rh
SR
s R/ \N
IN
IV’
t In the C-acylation according to process variant a) it has proved S advantageous to carry out the reaction in the presence of small amounts of cyanide, A low cyanide concentration can be ensured, for example, by the addition of acetone cyanohydrin.
c The rearrangement of the esters IV and IV’ can also advantageously be .o carried out under the action of cyanide ions and in the presence of a base.
Although the synthesis of the compounds of formula Ia and Ia’ outlined as reaction a) describes a process by which in principle a.l compounds included within the scope of formula la and Ia’ can be produced, for I reasons concerning economy and industrial scale production it may be appropriate to convert certain compounds of formula la and lI’ into other A ^derivatives included within the scope of formula I and Examples of such conversions, apart from reaction c) and are, for example, processes in which R 6 represents an ester, halogen or cyano radical.
These radicals can be converted analogously to the reactions illustrated hereinafter in Scheme 1 (IIa -4 IIb, IIc or IId) also even at the stage of compounds of formila I. Such derivatisation reactions are familiar to the person skilled in the art.
4 l;i 1 i 12 The above reactions are advantageously carried out in a solvent that is inert with respect to the reactions. Suitable inert solvents are hydrocarbons, such as benzene, toluene or xylene; ethers, such as diethyl ether, methyl isopropyl ether, glyme, diglyme; cyclic ethers, such as tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone; amides, such as dimethylformamide, N-methylpyrrolidone; sulfoxides, such as dimethyl sulfoxide; or chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or tetrachloroethane, alcohols, such as methanol, ethanol, isopropanol, propanol, butanol etc..
t In some cases it is also advantageous to use mixtures of solvents in the i as form of organic solvents in admixture with water.
4 4 t The reaction temperature can be varied within wide limits. Suitable reaction temperatures raige, for example, from -20°C to the reflux temperature of the reaction mixture. The reaction is preferably carried out at a temperature of from 0 C to 100 0
C.
In the case of reactions a) and b) a base is advantageously added.
S Suitable bases are, inter alia, sodium, potassium and calcium hydroxide, alkali metal and alkaline earth metal carbonates, amines, such as, for S example triethylamine, or heterocycles, such as pyridine, 4-dimethylaminopyridine, DABCO and also alkali metal hydrides.
Reactions a) and b) can also advantageously be carried out under phase transfer conditions in two-phase systems. Such reactions are familiar to the person skilled in the art (for example described in Dehmlow and Dehmlow, Phase Transfer Catalysis, Verlag Chemie, Weinheim 1983; a” W.E. Keller, Phase Transfer Reactions Vol. 1 and Vol. 2, G. Thieme Verlag, Stuttgart 1986, 1987).
The cyclohe”.anediones of formula II are either known or can be prepared analogously to processes known in the literature.
i J f -13- The following malonic ester synthesis is a general method of obtaining the cyclohexanediones II in which first of all, in accordance with the scheme below, the specifically substituted cyclohexanediones IIa, IIb or IIc can be produced from an aldehyde or ketone VI and acetone: Scheme 1 .R3/
VI
CH3- -C”
VII
\CH
3
VIII
COOR’
VIII C R 5
COOR’
Michael addition 4 It It St 4 1 R3
R
4 0 R’ R IIa (R 6 COOR’, R’ CI-C4alkyl) Hydrolysis IIa decarbocylation R3 R4 0 \R6 IIb (R 6
H)
The compounds of formula IIc in which the radicals R 3 to R 5 are as defined hereinbefore and R 6 is cyano can be prepared in a modification of reaction scheme 1 by Michael addition of cyanoacetic acid ester XII, in S’r which R 5 is as defined hereinbefore and R’ is C 1 -C4alkyl, to the ketone VIII, in which R 3 and R 4 are as defined hereinbefore.
CrI.
tell ii C 4. i C 4. C- Scheme 2 \CH3 R3/ \R
VIII
COOR’
NRs
N
R3- R 0
R
5 \R6 lic (R 6 CN) XIII Of the pyr~dinacarboxylic acid derivatives III, it is especially the acid chlorides that are preferred.
i I ~nWI i -clrc~-^ I 14 The pyridine-2-carboxylic acid chloride liIa may advantageously be prepared by a Pd-catalysed carbonylation reaction in accordance with the following reaction scheme 3: Scheme 3 R .y R 2 iI I N’ Hal
X
R’OH
Et 3
N
CO
Pd-cat RI \X
I
\N \COOH
R
1
R
2 R1 R 2 il -COOR’ N \COOR’ \N \CN Hydrolysis
XI
8181 i i i
I
*e 0 Ir *r *4 Halogenation e.g. SO 2 C12 or (COCl)2 R. R2 I I IJ XIV IIla (X halogen) In the above scheme, Hal is halogen (especially chlorine); R’ is C 1 -C4alkyl and Pd-Cat is preferably PdCl2(TPP)2 a triphenylphosphine complex of palladium.
The picolinic acid derivatives XI, IIIa and XIV mentioned in scheme 3 are valuable intermediates for the synthesis of the cyclohexanediones I of the invention. Most of these compounds are novel.
The invention thus also relates to the novel picolinic acid derivatives of formula XV 9*48
‘II
41 8 I r8
R
I
R
2 II I N/ CO-Y in which Y is OH; Ci-C4alkoxy; or halogen; and R 1 and R 2 independently of one another are each halogen; nitro; cyano; C 1 -Cshaloalkyl; Ci-C4alkyl; Ci-C4alkoxy; or Ci-C4alkyl-S(O)n-; and n is 0; 1; or 2; with the proviso that when Y is chlorine and the radical R I is bonded in position 3 and the radical R 2 is bonded in position 5, R 1 and R 2 are not simultaneously chlorine or simultaneously methyl, or when R’ is nitro R 2 is not methyl.
15 Preferred are picolinic acid derivatives of formula XV’ F 2
RI
1′ I XV’, co-Y in which Y is OH; C -C 4 alkoxy; or halogen; and R’ and R 2 independently of one another are each halogen; nitro; cyano; C 1
-C
4 haloalkyl; Cl-C 4 -alkyl; C -C 4 -alkoxy; or C -C 4 alkyl-S(O) and n is 0; 1; or 2; with the proviso that when Y is chlorine, R and
R
2 are not simultaneously chlorine or simultaneously methyl, or R nitro and R 2 methyl.
Especially preferred are the compounds of formula XV’ in which Y is OH; C -C 4 alkoxy; or halogen; R 1 is hydrogen; and R 2 is C1-C a alkoxy, C -C -haloalkyl; or cyano.
1 4 Also especially preferred are compounds of formula XV’ in which Y is OH; C 1
-C
4 alkoxy; or halogen; R is C 1 -C -alkoxy; C1-C 4 1: haloalkyl; or cyano; and R is hydrogen.
15 Of the compounds of formula XV, and the compounds XV’ mentioned as preferred and especially preferred, attention is drawn to the acid chlorides, that is to say those compounds in which Y is chlorine.
o 4 The invention also relates to a herbicidal composition for controlling undesired plant growth containing a compound of formula I 20 according to the invention together with further adjuvants and/or carriers.
The invention further relates to a process for the preparation of a 0 herbicidal composition according to the invention which comprises mixing a compound of formula I with the adjuvants and/or carriers.
The invention also relates to a method of controlling undesired plant growth at a locus, which method comprises treating the locus with a compound of formula I or a herbicidal composition according to the invention in a amount which effectively controls the undesired plant growth.
Another form of the invention relates to seeds when treated with a herbicidally effective amount of a compound of formula I or a herbicidal composition according to the invention.
The compounds of formula I are highly active ingredients for plants /336f 15A that at suitable rates of application are excellently suitable as selective herbicides for controlling weeds in crops of useful plants. That is to say, at such rates of application the active ingredients of formula I are distinguished by a good selective herbicidal property against weeds. In particular, cereals, such as rye, barley, oats, wheat and maize, but also other crop planes, such as sorghum, rice, cotton, sugar cane or soybeans or also permanent crops (such as, for example, vines or plantations) remain virtually undamaged at low rates of application. At increased rates of application the growth of the crop plants is influenced only to a small extent. If the rates of application are r 4 I 4 f r a I t ts C o t t a-
B^
r. 16 very high, the substances of formula I have total herbicidal properties.
The rates of application are generally from 0.001 to 4 kg, preferably from 0.005 to 2 kg of active substance per hectare.
At high rates of application the compounds of formula I can also be used as total herbicides. They are especially suitable for controlling weeds on paths, in public areas, on railway tracks or in other areas in which a total kill of the plants growing there is desired.
The selective herbicidal activity of the compounds of the invention is observed both in pre-emergence and post-emergence application. These compounds can therefore be used with equal success pre- or post-emergence in selective weed control.
,Advantageously, the compounds or compositions of the invention can be applied also to the propagation material of the crop plant. Seed cressi ,i ing, especially, may be mentioned here. Propagation material is seeds, o plantlets or other parts of the plant from which the crop plants can be reared. The invention also relates to the propagation material treated with an effective amount of a compound of formula I.
.oo The invention relates also to herbicidal compositions that contain a novel compound of formula I, and to methods for pre-and post-emergence weed control.
e The compounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants conventionally employed in the art of formulation, and are therefore formulateA in knovn manner e.g. into emulsifiable concentrates, directly sprayable or S dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
i A 17 The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant or extender, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents or extenders are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, othylene glycol monomethyl or monoethyl ether, ketones S such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrroj lidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable ;j oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical proper- Sties it is also possible to add highly dispersed silicic acid or highly S dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; S and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term “surfactants” will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.
18 Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 0’22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in th form of alkali metal S salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cs-Czzalkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of Slignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol V, sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalene- S sulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphati: alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
I.
?Li 1 1 r. atoms ir Lt.e alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene St f ,I 1 sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which S contain, as N-substituent, at least one CB-C 22 alkyl radical and, as f t further substituents, unsubstituted or halogenated lower alkyl, benzyl or S hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
I t V S Surfactants customary in the art of formulation are described, inter alia, in the following publications: “1986 International Mc Cutcheon’s Emulsifiers and Detcrgents”, Glen Rock, USA, 1986; H. Stache “Tensid Taschenbuch”, 2nd edition, C. Hanser Verlag, Munich/Vienna, 1981; M. and J. Ash. “Encyclopedia of Surfactants”, Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
The active ingredient preparations usually contain 0.1 to 95 preferably 0.1 to 80 of a compound of formula I, 1 to 99.9 of one or more solid or liquid adjuvants, and 0 to 25 of a surfactant.
Preferred formulations are composed especially as follows (throughout, percentages are by weight)
I
20 Emulsifiable concentrates: active ingredient: surfactant: liquid carrier: Dusts: active ingredient: solid carrier: Suspension concentrates: active ingredient: water: surfactant: Wettable powders: active ingredient: surfactant: solid carrier: Granulates: active ingredient: solid carrier: to 20 preferably to 30 preferably to 94 preferably to 10 to 20 to 85 0.1 to 10 preferably 0.1 to 1 99.9 to 90 preferably 99.9 to 99 Vt C
C
;t t Ct *r 0 *000C O 0
O
5 to 75 preferably 10 to 50 94 to 25 preferably 88 to 30 1 to 40 preferably 2 to 30 0.5 to 90 preferably 1 to 80 0.5 to 20 preferably 1 to 15 5 to 95 preferably 15 to 90 0.5 to 30 preferably 3 to 15 99.5 to 70 preferably 97 to 85 SWhereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The Sformulations can be diluted to a concentration as low as 0.001 active ingredient.
*too The compositions may also contain further additives such as stabilisers, S antifoams, viscosity regulators, binders, tackifiers and also fertilisers or other active ingredients for obtaining special effects.
The following Examples illustrate the invention.
1 c- 21 P. Preparation Examples: P.I. Compounds of formula I P.1.1. Reactions with cyclohexanediones of formula II 4,4 t I 4 44 4
I
‘444 ‘4 I 4v. a 1 44 41 *r 4 44..
*r 44 44 4 44 4 44 44 4 4 P.1.1.1. 2 -(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl)-cyclohexl-en-l-ol-3-one 4.9 g (20 mmol) of 3 -chloro-5-trifluoromethylpyridine-2-carboxylic acid chloride are added dropwise to a solution of 2.2 g (20 mmol) of 1,3cyclohexanedione and 7 ml (50 mmol) of triethylamine in 25 ml of dichloromethane, the temperature rising to 35 0 C. The whole is then stirred at room temperature for 15 hours to complete the reaction. The black suspension is diluted with 250 ml of dichloromethane, adjusted to pH 1 with IN HC1 at from 0 to 50, and washed twice with H20. The product is subsequently extracted with 5 NaHCO 3 solution, precipitated cold with 37 HC1, filtered with suction and dried. 4.0 g (63 of the title compound of formula Cl -CF3 I II
OH
are isolated in the form of crystals having a melting point of 102-105 0
C
(Compound No. 1.005).
P. 2-(5-trifluoromtIhvlpyrid-2-ylcarbonyl)-cyclohex-l-en-l-ol-3-one 20.4 g (85 mmol) of 5-trifluoromethylpyridine-2-carboxylic acid chloride are added dropwise at from 20 to 25 0 C to a solution of 9.5 g (85 mmol) of 1,3-cyclohexanedione and 24 ml (170 mmol) of triethylamine in 85 ml of dichloromethane. After the whole has been stirred for 4 hours at room temperature, 0.8 ml of acetone cyanohydrin is added and stirring is continued for a further 15 hours. The reaction solution is diluted with 200 ml of dichloromethane, adjusted to pH 1 with IN HC1 at from 0 to 5 0
C,
washed twice with water and extracted with 5 NaHCO 3 solution. The extract is washed with dichloromethane, adjusted to pH 1 with 37 HC1, and the precipitated product is filtered with suction and dried.
.4.4 44.
t ft *4 44* 4. 44« I ioL 1 ii
I
22 17.2 g (71 of the title compound of formula
\\CF
3
N=.
OH
are isolated in the form of crystals having a melting point of 95-97’C (Compound No. 1.010).
The compounds of Table 1 can be synthesised analogously to the aforedescribed preparation process.
P.1.1.3. 2 -(3-chloro-5-methylthiopyridin-2-lcarbonyl)-cyclohex–en_ 1-ol-3–one 4.4 g (0.048 mol) of 1,3-cyclohe.anedione and 10.6 g (0.048 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride are reacted analovously to P.1.1.1. and purified.
7.2 g (50.4 of the title compound of formula Cl\
OH
t Ct C C z t~ C C CC C C 44 .4 4 S 4 *0#4 0 09 *4 4 9′ 4 S 4 4.
are isolated in the form of crystals having a melting point of 113’C (decomp.) (Compound No. 1.018).
a.
4 94*# *0 4 54 .4 P.1.1.4. 3 -Chloro-5-methylsulfonyl-pyridin-2-yl-carbony1,)-cyclohex-len -l-ol- 3-on A scV’.ution of 5.6 g (50 mmol) l.3-cyclohexanedione and 14 ml (100 mmol) of trietylamine in 50 ml dichloromethane is added at 0 to 5’C to a suspension of 10.2 g (40 mmol) 3 -chlo ro- 5-me thyl sulf onyl-pyridine-2 -carboxylic acid chloride in 80 ml dichloromet’aane. After stirring for 3 hours at room temperature 0.5 ml of aceton cyanhydrin are added to the suspension thus obtained. Stirring is continued for 3 hours at room temperature. The dark brown suspension is then diluted with 200 ml i illl”pUPY–r 23 dichloromethane, adjusted to pH 1 with IN HC1, and washed twice with water. The product is subsequently extracted with 5 NaHC0 3 solution, precipitated cold with 37 HC1, filtered with suction and dried.
10.4 g (78.9 of the title compound of formula Cl\
SO
2
-CH
3 I II
N
.l
OH
are isolated in the form of white crystals having a melting point of >200 0 C (under decomp.) (Compound No. 1.020).
P.1.2.1. Preparation of 2-(3-chloro-5-methlisulfonylpyridin-2-yl- I carbonyl)-cyclohex-l-en-l-ol-3-one “k A solution of 4.1 g (0.02 mol) of 85 3-chloroperbenzoic acid in 50 ml S of dichloromethane is added dropwise to a solution of 3 g (0.01 mol) of 2-(3-chloro-5-methylthiopyridin-2-ylcarbonyl)-cyclohex-l-en-l-ol-3-one in 25 ml of dichloromethane with cooling at from 20 to 300C. The whole is then stirred at room temperature for 4 hours. The yellow suspension is filtered off from the chlorobenzoic acid and concentrated by evaporation on a rotary evaporator. The resulting mass is triturated with 50 ml of ether, filtered with suction and dried.
9 QA Sf r t Df S 1.8 g (51.6 of the title compound of formula Cl a II S OH 40 C OH are obtained in the form of crystals having a melting point of 150 0
C
(decomp.) (Compound No. 1.020).
24 Table I Compounds of formula 4 O~H R R2 R’ R 6 Comp. No. phys. data 4- 4 -4 4 4- 1.001 1.002 1.003 1.004 1 .005 1 .006 1 .007 1 .008 1 .009 1.010 1.011 01i2 1.013 1.014 1.015 1 016 1.017 1.018 1.019 1.020 1 4 44 4
I
I
I
Cl Cl
H
H
Cl
NO
2
H
NO
2
CF
3
H
OCH 3
CN
OCH 3
CN
Br S CH 3 Cl c 1, Cl
SOCH
3
SO
2
CH
3
H
H
Cl
H
F
F
CF
3
H
Cl.
CHl 3 Cl Cl
H
H
N02
H
Cl
H
Cl
H
CF
3
H
NO
2 Cl
H
CF
3 If
H
Cl Cl Cl
C)
S CH 3
SOCH
3
SO
2
CH
3 Cl
H
SO
2
CH
3
CH
3
F
CF
3
F
CF
3
F
CC1 3
H
CCl 3 cl1
H
Cl
H
Cl
H
CF3
H
NO
2 m.p. 144-146’C m.p. 106-107’C resin rn.p. 102-105%C 1.021 1.022 1.02 1.024 1.025 1.026 1.026 04? 1.028 1.029 1 .030 1.031 1.032 1.033 1.034 1-035 1.036 1.037 1.038 31.039 1.040 1.041 m.p. 95-97%C m.p. >113’C (decomp.) m.p. 134-136’C m.p. >150 0
C
(decomp.) m.p. 113-115%C m.p. 117-124 0
C
Fp. 0 3-103 0
C
i 25 ‘999 9 9 ‘9 9 @9 t 9 9 84 .999r 9 9 9 9, ft 9 9,9, 4.
4~ 99 Comp. No. R 1 1.042 N02 1.043 CF 3 1.044 H 1.045 OCH 3 .046 CN 1.047 OCH 3 1.048 CN 1.049 Br 1.050 SCh 3 1.051 S0 2
CH
3 1.052 Cl 1.053 Cl 1.054 Cl 1.055 SOCH3 1.056 S0 2
CH
3 1.057 H 1.058 H 1.059 Cl 1.060 H 1.061 F 1.062 F 1.063 CF 3 1.064 H 1.065 CC13 1.066 Cl 1.067 CC13 1.068 CH 3 1.069 Cl 1.070 Cl 1.071 H 1.072 H 1.073 Cl 1.074 NO, 1.075 H 1.076 NO 2 1.077 CY 3 1.078 ii 1.079 OCH 3 1.080 CN 1.081 OCH3 1.082 CN 1.083 Br 1.084 SCH 3 1.085 S0 2 CH3 1.086 Cl 1f087 Cl 1.088 Cl 1.089 SOCH 3 1.090 S0 2
CH
3 1.091 H 1.092 H 1.093 Cl R2 Cl
H
CF
3
H
H
Cl Cl Cl Cl Cl
SCH
3
~OCH
3
SO
2
CH
3 Cl
H
SO
2
CH
3
CH
3
F
CF
3
F
CF
3
F
CCl 3
H
ccl-..
Cl Cl
H
Cl
H
CF
3
H
NO
2 Cl
H
CF 3
H
H
C1 C1 C1
CI
C1 SCH3
SOCH
3 SO2CH3 Cl
H
S0 2C
H
CH
3
F
R
3 CH3 CH3
CH
3 CH3
CH
3
CH
3 CH 3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CR
3
CH
3
C
2 H5
C
2 Hs
C
2 H5
C
2 H5
C
2
H
C
2 Hs
C
2
H
5
C
2
H
5
C
2 Hs
C
2 HjB
C
2 H5
C
2 H5
C
2 H5
C
2 Hs
C
2 H5
C
2 H5
C
2
H
5
C
2
H
5
C
2
H
5
C
2 H5
C
2
R
5
C
2
H
5
C
2
H
5
C
2 Hs
C
2 H5 H4
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-I
R
6
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
phys. data m.p. 99-101 0
C
l_ L~ 26 Comp. No.
phys. data I I 1 1.094 1.095 1.096 1.097 1.098 1.099 1.100 1.101 1.102 1.103 1.104 1.105 1.106 1.107 t t 1.108 t c t1.109 1.110 1.111 1.112 1.113 1.114 1.115 1.116 1.117 1.118 1.119 1.120 1.121 1.122 1.123 1.124 1.125 1.126 1.127 1.128 1.129 1.130 1.131 1.132 1.133 1.134 1.135 1.1311 1.137 1.138 1.139 1.140 1.141 1.142 1.143 1.144 1.145
H
F
F
CF
3
H
CC13
CH
3
C’
Cl
H
H
C’
NO
2
H
NO
2
CF
3
H
OCH
3
CN
OCH
3
CN
Br
SCH
3 S0 2
CH
3 Cl Cl
SOCH
3 S02CH 3
H
H
Cl
H
F
F
CF
3
H
CC13 Cl CC13
CH
3 Cl
C’
H
H
Cl
NO
2
H
NO,
G? 3′
CF
3
F
CF
3
F
CC’
3
H
CC13 Cl
H
Cl
H
Cl
H
CF3
H
NO
2 Cl
H
CF3 if
H
Cl Cl Cl Cl cl
SCH
3
SOCH
3 S0 2
CH
3 Cl
H
SO2CH 3
CH
3
F
CF
3
F
CF
3
F
CCl 3
H
CC13 Cl
H
Cl
H
Cl
H
CF3
H
N02 Cl
H
C
2
H
C
2
C
2
C
2 Hs
C
2
C
2
H
C
2
H
n-C 31 n-C3H7 n-C 3 H7 n-C3H7 n-C 3 H7 n-C 3 n-C 3 H7 n-C 3 H7 n-C 3 H7 n-C 3 H7 n-C 3 H7 n-C3H7 n-C3 H’7 n-C 3
H’
n-C 3 H7 n-C3H7 f-C 3 H7 n-C 3 H7 n-C3H7 n-C 3 n-C 31H 7 n-C3H7 n-C 3 H7 n-CIH7 n-C 3 H7 n-C 3 H7 n-C3H7 n-C 31]’, n-C3H7 n-C3H7 n-C3H7 n-C 3
H’
n-C 3 n-C3H7 n-C3H7 i-C 3
H
i-C 3
H
i-C 3
H
i-C 3 H7 i-C 3
H
i-CH7 i-CH7 i-C 3 H7 m.p. 72-75 0
C
27 Comp. No.
1 .146 1 .147 1 .148 1 49 1 .50 1.151 1 .1 52 1.133 1.154 1.155 1.156 1 .157 1 .158 1.159 rftt 1.160 t t f ft1 1.161 1.162 t 1.163 1.164 1.165 1 .166 S 1.167 41.168 1.169 1.170 1.171 1 .172 1 .173 1.174 1.175 1.176 1.177 1.178 1.179 1 .180 1.181 1.182 1.183 1 1.184 1 .185 1.186 1 .18 7 1 .188 1 189 1.190 1.191 1.192 1.193 1 .194 1 .195 1.196 1.197
H
CN
OCH
3
CN
Br SCH3
SO
2
CH
3 Cl ci
C)-
SOCH
3 SO2 CH 3 Hi
H
Cl
H
F
F
CF
3
H
CC1 3 dl CC1 3
CH
3 Cl Cl
H
H
Gi
NO
2
H
NO
2
CF
3
H
0dH 3 rN OCH 3
CN
Br
SCH
3 SO2 CH 3 dl Cl Cl
SOCH
3
SO
2
CH
3
H
Hf Cl
H
F
i
R
2
CF
3
H
H
Cl Cl Cl Cl d Cl
SCH
3
SOCH
3 S0 2
CH
3 Cl
H
SO
2
CH
3 CH3
F
CF
3
F
CF
3
F
CC)-
3
H
CC13 Cl
H
cl Cl
H
CF3
H
N02 Cl
H
CF
3
H
Cl Cl Cl Cl
SCH
3
SOCH
3
SO
2
CH
3 Cl
H
SO2 CH 3 CH3
F
CF3
F
R 3 R 4 R5 c 3
H
7 H H
C
3
H
7 H H
C
3
H
7 H H
C
3
H
7 H H c 3
H
7 H H
-C
3 1-7 H H -c 3
H
7 H H
-C
3 1-7 H H
~-C
3 1- 7 H H
L-C
3 H-7 H H
L-C
3 1-7 H H-
L-C
3 1-7 H H L-C3H7 H H V-c 3 H7 H H i-37 H H L-c 3 H7 H H i-C31-7 H H i-C 3 H-7 H H i’-c 3
H
7 H H 1-c 3 H7 H H i-c 3
H
7 H H i-C 3 11 7 H H i-c 3
H
7 H H i-C 3 1-7 H H i-C 3 1-7 H H n-C 3 1-1 H H n-C 3 H-7 H H n-C 3 1-7 H H n-C 3 H7 H H n-C 3 H7 H H fl-C 3 H7 H H n-C 3 H7 H H n-C 3 1-7 H H n-C 3
H
7 H H n-C 3 H7 H H n-C 3 117 H H n-C 3 1-7 H H n-C 3 1-7 H H n-C 3 H7 H H n-C 3 H-7 H H n-C 3 H-7 H H n-C 3 1-7 H H n-C 3 H7 H H n-C 3 1-7 H H n-C 3 1-7 H H n-C 3 H7 H H n-C 3 H7 H H n-C 3 H7 H H n-C 3 1-7 H H n-C 3 1-7 H H n-C 3 H7 H H n-C 3 1-7 H H H 6
T
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Hi
H
HO C 1 1
COOC
2
COOC
2 1-H
COOC
2 1-1
COOC
2 1-1
COOC
2 C00C 2 171
COOC
2
COOC
2 1-1 COOd 2 1-1
COOC
2
COOC
2 dOOC 2 Hs
COOC
2 1-Hs
COOC
2 C0OC 2
HS
COOCz1-1
COOCZ
2 Hs C0OC 2 1-1 C00C 2
COOC
2 171
COOC
2
COOC
2
COOC
2 1-1 dOOd 2 phys. data i.p. 103-106 0
C
-28- Comp. No. R RRR 1 phys. data 1.198 F CF 3 n-C 3
H
7 H H COOC 2
H
1.199 CF 3 F n-C 3
H
7 H Hi COOC 2 1.200 H CC1 3 n-C 3
H
7 H H COOC 2
H
1.201 CC1 3 H n-C3H7 H H COOC 2
H
1.202 Cl CC1 3 n-C 3 H7 H H COOC 2
H
1.203 CC1 3 Cl n-C 3
H
7 H Hi COOC 2
H
1.204 CH 3 H n-C 3
H
7 H H COOC 2
H
1.205 Cl Cl i-C 3
H
7 H H COOCH 3 1.206 Cl H i-C 3
H
7 H H COOCH 3 1.207 H Cl i-C 3
H
7 H H COOCH 3 1.208 H H i-C 3
H
7 HH COOCH 3 1.209 Cl CF 3 i-C 3
H
7 H H COOCH 3 M-p. 91-92 0
C
1.210 NO 2 H i-C 3
H
7 H H COOCH 3 1.211 H NO 2 i-C 3
H
7 H H COaCH 3 S 1.212 NO 2 Cl i-C 3
H
7 H H COOCH 3 1.213 CF 3 H i-C 3 H7 H H COaCH 3 1.214 H CF 3 i-C 3
H
7 H H COOCH 3 1.215 OCH 3 H i-C 3
H
7 H H COOCH 3 1.216 CN H i-C 3 J17 Hi H COOCH 3 1.217 OCH 3 Cl i-C 3
H
7 H H COOCH 3 1.218 CN Cl i-C 3
H
7 H H COOCH 3 1.219 Br Cl j-C 3
H
7 H H COOCH 3 £1.220 SCH 3 Cl i-C 3
H
7 H H COOCH 3 1.221 S0 2
CH
3 Cl i-C 3
H
7 H H COOCH 3 1.222 Cl SCH 3 i-C 3
H
7 H H COOCH 3 1.223 Cl SOCH 3 i-C 3 H7 H H COOCH 3 1.224 Cl SO 2
CH
3 i-C 3
H
7 H H COOCH 3 1.225 SOCH 3 Cl i-C 3
H
7 H H COOCH 3 1.226 FO 2
CH
3 H i-C 3
H
7 H H COOCH 3 1.227 H SO 2
CH
3 i-C 3
H
7 H H COOCH 3 S 1.228 H CH 3 i-C 3 Hi 7 H H COOCH 3 1.229 Cl F i-C 3
H
7 H H COOCH 3 1.230 H CF 3 j-C 3
H
7 H H COOCH 3 1.231 F F i-C 3
H
7 H H COOCH 3 1.232 F CF 3 i-C 3 H7 H H COOCH 3 1.233 CF 3 F i-C 3
H
7 H H COOCH 3 1.234 H CC1 3 i-C 3
H
7 H H COOCH 3 1.235 CC1 3 H i-C 3
H
7 H H COOCH 3 1.236 Cl CC1 3 j-C 3
H
7 H H COOCH 3 1.237 CC1 3 Cl i-C 3
H
7 H H COOCH 3 1.238 CH 3 H i-C 3
H
7 H H COOCH 3 1.239 cl. Cl CH-3 H H COOCH 3 1.240 Cl H CH3 H H COOCH 3 1.241 H Cl CH 3 H H COOCH 3 1.242 H H CH 3 H H COOCH 3 1.243 Cl CF 3
CH
3 H H COOCH 3 1.244 NO 2 H CH 3 H H COOCH 3 1.245 H NO 2 CH3 H H COaCH 3 1.246 N0 2 Cl Cia H l H COOCH 3 1.247 CF 3 H CH 3 H H COOCH 3 1.248 H CF3 CH 3 H H COOCH 3 1.249 OCH 3 H CH 3 H H COOCH 3 29 Comp. No. I R 1 z R1 R 1.250 1 .251 1 .252 1 .253 1.254 1.255 1 .256 1 .257 1 .258 1.259 1.260 1.261 1 .262 1 .263 #tot 1.264 1.265 1.266 tt 1 .267 tx~1r 1.268 ftt 1.269 t C, i 1.271 t c i 1.271 ~f 1.272 1.274 1.274 1 .275 1 .276 1.277 1.279 to 1.280 1.281 1.282 a#64 1 .283 1.284 1.285 00*0. 1.286 1.287 a 1.288
CN
OCH 3
CN
Br S CH 3 S0 2
CH
3 Cl Cl
SOCH
3
SO
2
CH
3
H
H
C’1
H
F
F
CF
3
H
CC1 3 CC1 3
CH
3
C’
Cl
H
H
Cl
NO
2
H
NO
2
CF
3
U
OCH 3
CN
OCH 3
SCH
3 SO2 CU 3 Cl Cl Cl
SOCH
3
SO
2
CU
3
H
H
C’1
H
F
F
CF
3
H
Cl Cl Cl Cl Cl S CH 3
SOCH
3 SO2 CH 3 Cl1
H
SO
2
CU
3
(;H
3
F
CF
3
F
CF
3
F
CC’ 3
H
CC’ 3 Cl
H
Cl
H
Cl
H
CF
3
H
NO
2 Cl
H
CF
3
H
H
Cl Cl Cl Cl Cl
SCH
3
SOCH
3
SO
2
CH
3 Cl
H
SO
2
CH
3
CH
3
F
CF
3
F
CF
3
F
CU
3
CH
3
CU
3
CH
3
CH
3
CH
3
CH
3
CH
3
CU
3
CH
3
CH
3
CU
3
CH
3
CH
3 CU 3
CU
3
CU
3
CH
3
CH
3
CU
3
CH
3
CU
3
CH
3
CU
3 CH3
CU
3
CU
3
CU
3 CH3
CU
3
CH
3
CU
3
CU
3
CU
3
CU
3
CU
3
CH
3
CH
3
CH
3
CU
3
CU
3
CH
3
CH
3
CU
3
CU
3
CU
3
CU
3
CU
3 CH3 CH3
CU
3
CH
3
H
U
H
H
H
U
H
H
H
H
H
H
H
H
H
H
H
H
CH
CH
CH
CH
CH
CH
3
CU
3
CU
3
CU
3
CU
3 CU3
CH
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3
CU
3 R6CU
COOCH
3 COaCH 3
COOCH
3 COOCH 3 COaCH 3
COOCH
3
COOCH
3
COOCH
3 COO CU
COOCH
3
COOCH
3
COOCU
3
COOCH
3 COOCH3
COOCII
3
COOCH
3 COO CU 3
COOCH
3
COOCH
3
COOCH
3
COOCH
3
CQOCU
3
H
H
H
U
U
H
H
H
H
U
H
U
H
U
H
H
H
H
H
U
H
U
Iphys. data m.p. 131-133’C m.p. 95-98’C 1.289 1.290 1.291 1 .292 1.293 1.294 1.295 1.296 1.297 1.298 1.299 1 .300 1 .301 30 Comp. No. phys. data t t 1 .302 1.303 1 .304 1.305 1.306 1 .307 1.308 1 .309 1.310 1.311 1.312 1.313 1.314 1.315 1.316 1.317 1.318 S 1.319 1.320 1c32 1.322 1 .323 1.324 1.325 1 .326 1.326 1 .328 1 .329 4 1.330 1 .331 1.332 1.333 1.334 1.335 1 .336 1.337 1. 338 1.339 1.340 1.341 1.342 1 .343 1.344 1.345
H
Cdl 3
C)-
CC1 3 Gil 3 Gi Cl
H
H
Cl
NO
2
H
NO
2
CF
3
H
OCH
3
CN
OCH 3
CN
Br
SCH
3
SO
2
CH
3 Cl Cl Cl
SOCH
3
SO
2 Ci 3
H
H
Cl
H
F
F
CF
3
H
Gdl 3 Cl CC1.
3 Gil 3 Cl Cl
H
H
Gi N02
H
NO
2
CF
3
H
OGH 3
CN
OCH 3 CC’ 3
H
CC1 3 Cl
H
Cl1
H
Cl
H
CF
3
H
N0 2 Ci
H
CF
3
H
H
Cl Ci1 Ci1 Ci Ci
SCH
3
SOCH
3
SO
2 CGi 3 Cl
H
SO
2 CGi 3
CH
3
F
CF
3
F
CF
3
F
CCc 3
H
Cdl 3 Cl
H
Ci
H
Cl
H
CF
3
H
NO
2 Cl
H
CF
3
H
H
Ci Gil 3 Gil 3 GHl 3 Gil 3 Gil 3 Gil 3 Gil 3
CH
3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3
GH
3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3
GH
3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 C6H 5 Gs6li
G
6
H
5
G
6 il 5 C6H 5 GsHs G611 5
G
6
H
5 GsH5 GsH5
G
6 Hs
G
6 H5 C6Hs Gil 3 Gil 3 Gil 3 GHl 3 Gil 3 Gil 3 Gil 3 Gi 3 Gil 3 Gil 3 Gil 3 Gil 3 Gi 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gi 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3 Gil 3
H
H
H
H
H
H
H
11
H
H
H
H
H
H
H
H
COOC
2
H
GOOC
2
H
GOOC
2
H
COOG
2 Hs
COOG
2
HS
COOC
2 His
GOOC
2
GOOG
2
GOOG
2
GOOG
2
GOOC
2 GOOC2Hs
COOC
2
GOOC
2
GOOG
2
COOC
2
GOOG
2
COOC
2
GOOG
2
H
GOOC
2 Hs
COOG
2
GOOC
2
H
GOOC
2
GOOG
2
GOOG
2
GOOG
2
COOC
2
GOOG
2
GOOC
2
GOOC
2
H
H
H
H
H
H
H
H
H
H
H
HI
H
m.p. >150’C (decomp.) 1.346 1.347 1 .348 1 .349 1.350 1.351 1 .352 1.353 U 31- Gomp. No. R 1
R
R R 2
R
6 phys. data 1.354 GN Cl C 6
H
5 H H H 1.355 Br Cl C6H5 H H H 1.356 SCH 3 Cl C 6 Hs H H H 1.357 S0 2
CH
3 Cl C6Hs H H H 1.358 Cl SCH 3
C
6 Hs H H H 1.359 Cl SOCH 3
C
6 Hs H H H 1.360 Cl SO 2
CH
3
C
6 Hs H H I-i 1.361 SOCH 3 Cl CsH5 H H H 1.362 S0 2
CH
3 H C6Hs H H H 1.363 H S0 2
CH
3 C6H 5 H H H 1.364 H CH 3 C6H5 H H H 1.365 Cl F C 8 H5 H H H 1.366 H CF 3 C6Hs H H H 1.367 F F sH 5 H H H 1.368 F CF3 CsH 5 H H H 1.369 CF 3 F CsH5 H H H 1.370 H CC1 3
C
6
H
5 H H H 1.371 CC1 3 H CsHs H H H 1.372 Cl CC1 3 CsH 5 H H H 1.373 CC13 Cl C 6
H
5 H H 1.374 CH 3 H C 6
H
5 H H H 1.375 Cl Cl H H CH 3
CH
3 C1 IH H H CH 3
CH
3 1.377 H Cl H H CH 3
CH
3 1.378 H H H H CH 3
CH
3 1.379 Cl CF 3 H H CH 3 Gi 3 1.380 NO 2 H H H CH 3
CH
3 1.381 H N02 H H ICH 3 iCH 3 1.382 N0 2 Cl H H CH 3
ICH
3 0 4 4 1.383 CF 3 H H H CH3 CH3 1.384 H CF 3 H H CH 3 ICH3 1.385 0CH 3 H H H iCH 3 CH3 1.386 CN H H H CH 3
CH
3 1.387 OCH 3 Cl H H CH3 Gi 3 1.388 CN Cl H H iCH 3 CH3 1.389 Br Cl H H Gil 3
CH
3 1.390 SCH 3 Cl 11 H iCH 3 ICH3 1. 391 So 2
CH
3 Cl H H CH 3
CH
3 1.392 Cl SGH 3 H H IH CH3 1.393 Cl SOCH 3 H H 33,H Gl 3 1.394 cl S02CH 3 H H CH 3
CH
3 1.395 SOCH 3 Cl H H CH 3
C
3 1.396 S0 2
GH
3 H H H CH 3 GI 3 1.397 H S02CH 3 H H iCH 3 Gi 3 1.398 H iCH 3 H H CH 3 iCH 3 1.399 Cl F H H CH 3 CH3 1.400 H CF3 H H Gil 3 iCH3 1.401 F F H H CH 3 Glil 3 1.402 F CF 3 H H CH 3 iCH3 1.403 CF 3 F H H CH3 CH3 1.404 H CC13li CH3 CH3 1.405 CC1 H H H CH 3
CH
3 32 Comp. No. phys. data F 4- 4- 4 4- F F 1.406 1.407 1.408 1.409 1.410 1.411 1.412 1.413 1.414 1.415 1.416 1.417 1.418 1.419 I 1.420 1.421 1 1422 1.423 1.424 1.425 1.426 1.427 1.428 1 .429 1 .430 1 .431 1 .432 1 1.433 1.434 1.435 1.436 1 .437 1.438 1 .439 1 .440 1 .441 1.442 0 &A 1.443 1.444 1 .446 1 .447 1 .448 1 .449 1.450 1 .451 1.452 1.453 1.454 1.455 1 45 6 1 .457 Cl3
CH
3 Cl Cl
H
H
Cl
NO?
H
NO
2
CF
3
H
OCH 3
CN
OCH 3
CN
Br
SCH
3
SO
2
CH
3 Cl Cl
SOCH
3 H0CB
H
Cl
H
F
F
CF
3
H
cc1 3 Cl CC’ 3
CH
3 Cl Cl
H
H-
Cl
NO
2
H
NO
2
CF
3
H
OCH 3
CN
OCH 3
CN
Br CC1 3 Cl
H
Cl
H
Cl
H
CF
3
H
NO
2
C’
H
CF
3
H
H
C’
Cl Cl Cl Cl
SCH
3
SOCH
3
SO
2
CH
3 Cl
H
SO
2
CH
3
CH
3
F
CF
3
F
CF
3
F
CC1 3
H
CCl .3 Cl
H
Cl
H
Cl
H
CF
3
H
NO
2 Cl
H
CF
3
H
H
Cl Cl cl
H
H
H
C
6 Hs-CH 2
C
6 Hs -CH 2
C
6 Hs-CH 2 C6Hs-CH 2
C
6 Hs-CH 2 CGH5-CH 2
C
6 Hs-CH 2 C6H5-CH2- C6 HS-CH 2 C 6 H 5-Cl1 2
C
6 H15 -CH 2
C
6 H5-CH 2
C
6
H
5 -C11 2 C6H5-CH 2
C
6 H5-CH2-
C
6 H5-CH 2
C
6 11 5
-CH
2 C6H 5
-CH
2
C
6 115-CH 2 C6Hs-CH 2
C
6
HS-CH
2 C6Hs-CH 2 C6H5-C11 2
C
6 Hs-CH 2
C
6
HS-CH
2
C
6 115-CH 2 CGHs-C11 2 C6B5-CH 2
C
6
HS-CH
2
C
6 11 5
-CH
2 CGH5-C11 2 C6H5-C11 2 4-Cl-C 6 H4 4-Cl-C 6
H
4 4-Cl-C 6
H
4 4-Cl-C6H.
4-Cl-C 6
H
4 4-Cl-C 6 H4 4-Cl-C6H4 4-Cl-C 6
H
4 4-Cl-C 6 Hi 4-C1-C 6
H.
4-Cl-C~h 4 4-Cl-C 6 H4 4-Cl-C 6 H4 4-Cl-C 6 H4 33 Comp._No.
1.458 1 .459 1 .460 1 .461 1 .462 1.463 1.464 1.465 1 .466 1 .467 1.468 1 .469 1 .470 1 .471 ftr1 1 .472 1.473 1.474 1 1.475 1 .476 1.477 1.478 1 .479 1.480 1 .481 1 .482 1 .483 1 .484 1.485 1 .486 1 1.487 1′ 1.488 1 .489 1.490 1 .491 1.492 1.493 1.494 1.495 1.496 1 1.497 1.498 1.499 1 .500 1 .501 1 .502 1.503 1.504 1 .505 1 .506 1 .507 1 .508 1 .509
SCH
3
SO
2 CH3 Cl Cl Cl SOCH3 SO2CH3
H
H
Cl
H
F
F
CF
3
H
cl
CH
3 Cl Cl
H
H
01
NO
2
H
NC6,
CF
3
H
OCHi 3
CN
OCH 3
ON
Br SCH3
SO
2
CH
3 Cl Cl Cl S0CH3 SO H
H
Hl
CH
H
F
F
CF
H c CC13 Cl Cl
SCH
3
SOCH
3 Cl
H
OH
3
F
CF
3
F
CF
3
F
0013
H
0013 Cl
H
Cl1
H
C 1
H
CF
3
H
NO
2 Cl
H
CF
3
H
H
Cl, Cl Cl Cl Cl
SCH
3
SOCH
3 SO2OH 3 Cl
H
SO
2 CH3 CH3
F
CF
3
F
CF
3
F
001 3
H
0013 Cl R3l- 6
H
4-Cl-C 6
H
4 4-Cl-C 6
H
4 4-Cl-C 6
H~
4 4-Cl-C6H 4-C1-C 6 H4 4-Cl-C 6 H4 4-Cl-C6H 4 4-Cl-C 6
H+
4-Cl-C6H4 4-Cl-CGH4 4-C1-C 6 H4 4-Cl-C 6 H.4 4-Cl-C 6
H.
4-Cl-C 6
H
4 4-Cl-C 6 H4 4-Ci-OsH4 4-Cl-C 6
H
4 4-Cl-C6H
OH
3
OH
3 CH3 CH3
CH.
CH~
CH3 CH3 CH3 CH3 CH3
OH
3 CH3 OH3
OH
3 CH3 CH3
OH
3 CH3
OH
3 CH3 CH3
OH
3
OH
3 CH3 CH3 CH3 CH3
OH
3 CH3 CH3 CH3
H’
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
R’
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3 OH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 OH3 CH3 CH3 CH3 CH3
CH
3 CH3 CH3 CH3 CH3
CH
3 OH3 CH3 CH3 CH3 CH3 CH3
OH
3 CH3 CH3 CH3 CH3 CH3 R 6
H
H
Hi
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
phys. data -34 comp. No. R
R
3 R R5 R6 phys. data 1.510 1.511 1 .512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1 .520 1 .521 1 .522 1 .523 S 1.524 1~ .525 1.526 1.527 S1.528 1 .529 *1.530 1~ .531 1 1.532 1 .533 1 .534 1 .535 1 .536 S 1.537 1. .538 1.539 1.540 1 .541 1.54 1.542 1 .544 1 .545 1.546 1.547 1.548 1 .550 1 .551 1 .552 1 .553 1.554 1 .555 1.556 1 .557 1 .558 1 .559 1 .560 1.561 Cli 3 Cl Cl
H
H
Cl N2
H
NO2 CF3
H
OCH 3
CN
OCH 3
CN
Br S CH3
SO
2 CH3 Cl Cl Cl SOCHI3 Sr -!CH 3
H
H
Cl
H
F
F
CF3
H
CCI 3 Cl CC13 CH3 Cl Cl
H
H
Cl
NO
2
H
N02 CF3
H
OCH 3
CN
OCH 3
CN
Br SCH3 S0 2 CH3
H
Cl
H
Cl
H
CF
3
H
N0 2 Cl
H
CF
3
H
H
Cl Cl ClJ cl Cl SCH3
SOCH
3 S0 2
CH
3 Cl
H
S0 2 CH3 CH3
F
CF
3
F
CF
3
F
CCla3
H
CCl 3 Cl
H
Cl
H
Cl
H
CF
3 Hi N02 Cl.
F,
CIF3
H
H
Cl Cl Cl cl Cl
CH
3
H
H
H
H
H
H
H1
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Hi
H
H
H
H
H
H
H
H
H
CH
CH
CH
3
CH
3 CH3
CH
3
CH
3
CH
3
CH
3 CH3
CH
3
CH
3 CH3 CH3
CH
3 CH3 CH 3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H 1
H
H
H
H
H
H
H
CH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
Comp. No. R 1 R 3 R’ R phys. data 1.562 Cl SCH 3
CU
3 H H CN 1.564 Cl SOCH 3
CU
3 H H CN 1.565 SCH 3 S0C CHU 3 H H CN 1.6 OH lCU 3 H H CN 1.6 0C3 HCU 3 H H CN 1.5670 H S0C 3 CH3 H H CN 1.569 Fl F CH 3 H H CN 150 HCF 3
CU
3 H H CN 1.573 F F CH3 H H CN 1.574 H CFl 3
CU
3 H H CN 1.575 CF3 H CU 3 H H CN 1.7 C3 CU 3 H H CN 1 1.579 CC1 Hl CH H H COH S 1.580 Cl C1 CH3 H H CNH 1 .571 HC1 Cl CH3 H H CNH v :t 1.578 H H CH 5 H H CNH 1 .583 Cl CF 3 CsHs H H COOCH 3 mp 1.584 NO 2 H C 6 H5 H H COaCH 3 deop 1.586 H0 Cl C6H5 H H COOCH 3 .587 CF H C 6 H5 H H COOCH 3 r 1.588 Hl CF 3
C
6 H5 H H COOCH 3 MP 1.589 NC02 H C 6 H5 H H COaCH 3 o 1.591 HCU C0 C6H5 H H COOCH 3 1.592 N Cl C 6
H
5 H H COaCH 3 1.593 Br3 H C 6 Hs H H COOCU3 1.595 SH 3 Cl C6s H H COOCH 3 1,589 Cl CH 3 H C6Hs H H COOCH 3 0 1.597 Cl OH 3 CsHS H H COOCH 3 1.598 OC SOCH C6H5 H H COOCH 3 1.599 SCH 3 Cl C 6 Hs H H COOCH 3 1.600 BrCH Hl C6H5 H H COOCH3 1.601 SH3 S~CH CsH5 U H COOCH3 1.602 S2H3 CH C6H5 H H COOCH3 1.56 Cl FCH C05 H H COOCH3 1.604 Hl SCF 3 C6H 5 H H COaCH 3 1 .65 Fl F0C C6H5 H if COOCH3 1.606 FOH CF 3 C6H 5 H H COOCH 3 1.607 S0CF 3 F C6H 5 H H COOCH3 1.602 H CH 3 CsH 5 H H COOCH 3 1.604 CH HF CsH5 H H COaCH 3 1.60 C CF 3 C6H 5 HH COOCH 3 1.611 CC1 3 Cl COSs H H COOCH 3 1.612 CH 3 HI C6H5 H H COaCH 3 7 36 Comp. No. R 6 1phys. data 1.613 1.614 1.615 1.616 1.617 1.618 1.619 1 .620 1 .621 1 .622 1 .623 1 .624 1.625 1 .626 1 .627 1. 628 4 1.629 1 1.630 1.631 S 1.632 1 .633 1.634 1 .635 1 .636 1.637 1 .638 1 .639 1 1.640 1 .641 1 .642 1 .643 41 1.644 1.645 1 .646
H
H
Hi C0 2
H
C0 2
H
C0 2
H
C0 2
H
CO
2
CH
3 CO2CH5
CO
2
NH
2
CN
C0 2
H
CO
2
CH
3 C0 2
H
CO
2
CH
3
CO
2
CH
3 C0 2
H
Cl
H
Cl Cl Cl Cl
SC
2
H-‘
SOC
2
HS
SO
2
C
2
HS
H
Cl Cl Cl Cl Cl Cl
H
SCH
3
SOCH
3
SO
2
CH
3
H
H
H
H
H
H
H
H
C H 3
CH
3
C
2
HS
C
2 H5 Br Br
CF
3
CF
3 OCH 3 SC 2 Hs
SOC
2 B5 S02 C 2 H5 Cl Cl Cl
SO
2
C
2 H5
SO
2
C
3
B
7 (i)
SOC
3
H
7 (i)
SC
3
H
7 (i)
OCH
3 0C 3
H
7 (i) Br
OCH
3
H
H
H
H
CH 3
H
H
H
H
H
H
H
H
H
H
H
H
CH
3
CH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH
CH
H
H
H
H
CH
CH
H-
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH
3
CH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
m.p. >140′ Z Tn.p. >150′ Z m.p. 65-70’C m.p. 79-85’C 44 4 06* -37- P.1.2. Preparation of salts of formula I P.1.2.1. Sodium salt of 2-(3-chloro–5-trifluoromethylpyridin-2-ylcarbonyl)-cyclohex–1-en-1-ol-3-one IJI 3.2 g of 3-chloro-5-trifluoromethylpyridin-2–yilcarbonyl) -cyclohex-1 en-1–ol-3-one are dissolved in 20 ml of methan” 0.54 g of sodium methoxide is added and the whole is stirred at room temperature for minutes and then concentrated to dryness on a rotary evaporator. The residue is triturated with diethyl ether, filtered and dried.
The title compound of formula Cl\ /CF
N
0 ONa jis isolated in quantitative yield in the form of a colourless solid j (Compound No. 2.006).
iThe saUts of Table 2 can be synthesised analogously to the above 4 I preparation pr~ocesses.
r p a, fr..* .9 a a a a p a, t G a a a a a a, a, a, a t a a at a 38 Table 2 Compounds of formula R 3′ R I0+
R
R 6Y Comp. No.
phys. data 4- 4 4- 4 4 4 t
I(
2.001 2.002 i:003 2.004 2.005 2.006 2.007 2.008 2.009 2.010 2.011 2.012 2.013 2.014 2.015 Na 1/2 Ca 2 0
NH(CH-
3 3
NH(C
2
H
5 0H)30 Na Li 1/2 Ca 20 NH(CH3 )3
NI-(C
2
H
5 Na Li 1/2 Ca 20
NH(CH-
3 3 NH(C2
M
5 OH)3 3 colourless solid 39 Comp. No. R 1 R2 R3 R4 R 5
R
6 IA® phys. data 2.016 H 140 2 H H H H NaI 2.017 H NOz H H H H Li 2.018 H NO 2 H H H H 1/2 Ca 2 2.019 H NO4 2 H H H H NH(CH 3 3 2.020 H NO 2 H H H H NH(C 2
H
5
OH)
3 2.021 H H H H H H Na 2.022 H H H H H H Li(D 2.023 H H !Hi H H H 1/2 Ca 2 0 2.024 H h H H H H NH(CH 3 3 2.025 H H H H H H NH(CzH 5 H)3 0 2.026 Cl CC1 3 H H H H Na 2.027 Cl CC 3 H H H H Li 2 2.028 cl CC1 3 H H H H 1/2 Ca 2.029 Cl CC1 3 H H H H NH(CH 3 3 2.030 Cl CC1 3 lH H H H NH(C 2 H50H) 3 0 2.031 F CF 3 H H H H Na 2.032 F CF 3 H H H H Li 0 2.033 F CF 3 H H H H 1/2 Ca 2 0 2.034 F CF 3 H H H H NH(CH 3 3 2.035 F CF 3 H H H H NH(C 2
H
5
OH)
3 2.036 Cl Cl CH 3 H H H Na® 2.037 Cl Cl CH 3 H H H Li® r~ 4
L
R2 R3 0 C 0 C 6 CC
C
~1 40 Comp. No. I R’ 2.038 2.039 2.040 2.041 22.04 A 3 2.044! 2.045 2.046 2.047 2.048 2.049 2.050 2.051 2.052 2 053 2.054 2.055 2.056 2.057 2.058 2.059 Cl Cl Cl Cl Cl Cl Cl
C’
NO
2 N0 2
NO
2
NO
2
NO
2
H
H
H
H
H
H
H
H
H
R 4 5 R C-phys. data H3 H H H 1/2 Ca 2 H3 h l H NH(CH 3 3 0 H3 H H. NH(C 2
H
5
OH)
3 H2 H H H Na H3 H H H Li H3 H H H 1/2 Ca 2 13 H H H NH(CH 3 3
G
H13 H H H NH(C 2
H
5 0H) 3 0 H3 H H H Na H3 H H H Li@ 13 H H H 1/2 Ca 2 0 H3 H H H NH(CH 3 3 0 H3 H H H NH(C 2
H
5 0H) 3 0 33j H H1 H Nao H3 H H H Li 0 H3 H H h’ 1 2Ca 2 H3 H H H NH(CH 3 3 H3 Il H H NH(C 2 H5OH) 3 0 H3 H H H Na 0 H3 H H H Li 0 H3 H H H 1/2 Ca 2 H I H NH(CH 3 )3 ~~41 Cop oa. r R3 a Rs R*Mp .dt 2. 6 08 CC1 CH H a 2.6 l aM3 C H H H*i 2.06 .l aC1 CH S. 12C 2.060 Hl H1 OH 3 H H H NH(C 2
H
5 0H) 3
E
2.066 CF CF 3
CH
3 H H H Na E 2.062 CF CI 3
CH
3 H H H Li 0 2.068 Cl CF 3
CH
3 H H H 1/2 Ca2( 2.064 Cl CFl 3
CH
3 H H H NH(CH 3 3
O
2.070 Fl C1 3
CH
3 H H H NH(C 2
H
5
OH)
3 2.066 Fl CF 3 nCH H H H Na 2.0672 Fl CF nCH7 H H H Li 2.068 Fl CF 3 nCH H H H 1/2 Ca 2 0 2.069 Fl CF 3 nCH H H H NH(CH 3 3 2.070 Fl CF nCH H H H NH(C 2 HsOH) 3 2.076 cl Cl3 n-C 3
H
7 H H H Na®E 2.072 Cl Cl3 n-C 3
H
7 H H H Li 0
E
2.078 Cl Cl3 n-C 3
H
7 H H H 1/2 Ca 2 0 2.074 Cl Cl3 n-C 3 H7 H H H NH(CH 3 3 0 2.075 Cl Cl3 n-C 3
H
7 Hi H H NH(C 2
H
5
OH)
3 2.081 IN02 H n-C3H 7 H H H Na® 2.082 N2 H n-3H7 H H Li.
2.083 N02 H R 5 6 I iOIphs dt 2.084 N02 H n-C3H7 H H NBCH) 2.085 N02 H n-C3H7 H H H N, NI(:2H0H)38 2.086 H N02 n-C3H7 H H H ll;: A,2.087 H N02 n-CH7 H H H Li 2(D 2.088 H N02 n-C3li7 H H H 1/2 Ca 2.089 H N02 n-C3H7 H H NH(CH3 9 *2.090 H N02 n-C3H7 H H 9 H 0 NH(C95oH 2.091 H H n-C3H71 H H H Na 2.092 H H n-CH7 H H H Li 2.083 NoH H n-C3H7 H H H 1/2 Ca 2.084 N H n-C 3
H
7 H H H NH(CH 3 3 2.085 NH H n-C3H7 H H H NH(C 2 H50H) 3 (Dj 2.086 H CC1 n-C 3 H7 H H H 1 Na 2.087 H CC13 n-C 3
H
7 H H H Li 2.088 H CC13 n-C 3
H
7 H H H 1/2 Ca 2.089 H CC13 n-C 3
H
7 H H H NH(CH 3 3 0 2.100 H 2 CC n-C 3
H
7 H H H NH(C 2 H50H)3 2.101 F CF3 n-C 3
H
7 H H H Na 0 2.102 F CF3 n-C3H7 H H H Li 2.103 F CF3 n-C 3
H
7 H H H 1/2 Ca Cop No ess R2 R3 R4R.R6 m hdt *l 4l i3H HH a G) 2.10 al -l *-37 H Ca 2.109 Fl CF n-C 3
H
7 H H H NH(CH 3 3 2.110 F CF n-C 3
H
7 H H H NH(C 2
H
5
OH)
3
I
2.111 Cl Cl3 i-C 3
H
7 H H H Na 2.107 Cl CF3 i-C 3
H
7 H H H Li( 2.108 Cl Cl3 i-C 3
H
7 H H H 1/2 Ca 21 2.109 Cl Cl3 i-C 3
H
7 H H H NH(CH 3 3 2.110 Cl Cl3 i-C 3
H
7 H Hi H NH(C 2 HsOH) 3
G®
2.111 N02 CF i-C 3
H
7 H H H Na®( 2.112 N02 CF i-C 3
H
7 H H H Li 2.113 N02 CF i-C 3
H
7 H H H 1/2 Ca 2 2.114 N02 CF i-C 3
H
7 H H H NH(CH 3 3 2.115 N02 CF i-C 3
H
7 H H H NH(C 2 H5OH) 3 2.11 NO H0 i-C 3
H
7 H H H Na G 2.117 NO H0 i-C 3
H
7 H H H Li® 2.121 H N0 2 i-C 3
H
7 H H H Na C 2 2.124 H NO 2 i-C 3
H
7 H H H NH(CHa) 3 2.2* oc H H H a (D0 2.12 H H C-37 H Ca 2( 2.135 H NO i-C 3
H
7 H- H H NH(C 2
H
5
OH)
3 2.126 Hl HC i-C 3
H
7 H H H Na 0 2.12 l H1 i-C 3
H
7 H H H Li 0 2.128 H HC1 i-C 3 H7 H H H 1/2 Ca 2 0 2.129 l HC1 i-C 3
H
7 H H H NH(CH 3 3 0 2.130 Hl H1 i-C 3
H
7 H H H NH(C 2
H
5
OH)
3 0
(D
2.131 CF Cd 3 i-C 3
H
7 H H H Na 2.132 Cl Cd 3 i-C 3
H
7 H- H H Li 0 2.138 Cl CFl3 i-C 3 Hi 7 H H H 1/2 Ca 2 0 2.134 CF CFl 3 i-C 3
H
7 H H H NH(CH 3 3 0 2.135 CF CF 3 i-C 3
H
7 H H H NH(C 2 H5OH) 3 0 2.136 Fl CF 3 iCH H H H Na 2.137 Fl CF 3 iC6H H H H Li 0 2.13 Fl CF iC6H H H H 1/2 Ca 2 2.139 Fl CF 3 i-C 3 H H H H NH(CH 3 3 2.145 Fl CF 3 iC6H H H H NH(C 2
H
5
OH)
3
E
0 2.146 Cl CF 3
C
6
H
5 H lH H Na 0 45 Comp. No. R 1 R 2 R 3 R’ R 5 HR6 m(D phys. data 2.147 Cl CF 3
C
6
H
5 H H H Li 2.148 Cl CF 3 C6H 5 H H H 1/2 Ca 2 2.149 Cl CF 3
C
6 H5 H H H NH(CH 3 )3 0 2.150 Cl CF 3
C
6
H
5 H H H NH(C 2
H
5
OH)
3 0 2.151 NO 2 H C 6 Hs H H H Na 2.152 NO 2 H CsH 5 H H H Li 0 2.153 NO 2 H C 6
H
5 H H H 1/2 Ca 2 2.154 NO 2 H CsH5 H H H NH(CH 3 3 0 2.155 NO 2 H C 6
H
5 H H H NH(C 2
H
5
OH)
3 0 2.156 H N02 C 6
H
5 H H H Na 2.157 H NO 2
C
6
H
5 H H H Li 2.158 H NO 2
C
6
H
5 H H H 1/2 Ca 2
D
2.159 H N02 C6H 5 H H H NH(CH 3 3 2.160 H NOz C 6
H
5 H H H NH(C 2
H
5
OH)
3 2.161 H H C6Hs H H H Na 2.162 H H C6H 5 H H H Li 0 2.163 H H CsHs H H H 1/2 Ca21 2.164 H H C6H 5 H H H NH(CH 3 3 0 2.165 H H C 6 Hs H H H NH(C 2 H50H) 3 0 2.166 Cl CC1 3
C
6
H
5 H H H Na 2.167 Cl CC1 3
C
6
H
5 H H H Li 2.168 Cl CCl 3
C
6
H
5 I;H H H: i /2 Ca Cop No Ra R2 R R Dpy.dt 2.17 F 65 HH a2 2.169 Cl CFl 3
C
6
H
5 H Hi H NH(CH 3 3 0 2.170 Cl CF 3 CrH 5 H H H NH(C 2 HsOH) 3 0 2.171 Fl CF CH3 CH H H Na 0 2.172 Fl CF 3
CH
5 H3 H H Li 0 2.174 Fl CF CH3 CH H H NH(CH 3 3 2.185 Fl CF CH3 CH H H NH(C 2
H
5 0H) 3 0 2.176 Cl Cl3 CH 3
CH
3 H H Na 0 2.177 Cl Cl3 CH 3
CH
3 H H Li 2.1783 Cl Cl3 CH 3
CH
3 H H 1/2 Ca 2 2.179 Cl CF3 CH 3
CH
3 H H NiH(CH 3 3 0 2.185 Cl Cl3 CH 3
CH
3 H H NH(C 2
H
5
OH)
3 2.181 N02 CF CH 3
CH
3 H H Na® 2.182 N02 CF CH 3
CH
3 H H Li 0 2.183 N02 CF CH 3
CH
3 H H 1/2 Ca2( 2.186 NO 2 H CH 3
CH
3 H H Na 0 C3) 2.190 N0 2 Hi CH 3
CH
3 H H NH(C 2
B
5
OH)
3
I
‘4 ‘4 47 Gomp. No. R R2 R3 R’ R5 R6 phys. data 2.191 H NO 2
CH
3
CH
3 H H Na 2.192 H NO 2
CH
3
CH
3 H H Li 2.193 H NOz GH 3
CH
3 H H 1/2 2.194 H NO 2
CH
3
CH
3 H H NH(CH 3 3 2.195 H NO 2 Ci 3
CH
3 H H NH(C 2
H
5 0H) 3 2.196 H H CH 3
CH
3 H H Na 2.197 H H CH 3
CH
3 H H Li 2.198 H H CH 3
CH
3 H H 1/2 Ca 2 2.199 H H CH 3 Ci 3 H H Ni(CH 3 3 0 2.200 H H CH 3
CH
3 H H NH(C 2 HsOH) 3 0 2.201 Cl CC1 3
CH
3
CH
3 H H Na 2.202 Cl CC1 3
CH
3
CH
3 H H Li 0 2.203 Cl CC1 3 CH3 CH 3 H H 1/2 Ca2G 2.204 Cl CC13 CH 3
CH
3 H H NH(CH 3 3 2.205 Cl CC1 3
CH
3 Gi 3 H H NH(C 2
H
5
OH)
3 0 2.206 F CF 3
CH
3
CH
3 H H Na 0 2.207 F CF 3
CH
3
CH
3 H H Li 0 2.208 F CF 3 CHi 3
CH
3 H H 1/2 Ca 2.209 F CF 3
CH
3
CH
3 H H NH(CH 3 3 0 2.210 F CF 3
CH
3
CH
3 I H NH(C 2
H
5 0H) 3 0 2.211 Cl Cl CH 3 H CH H Na 0 2.212 Cl Cl CH 3 H CH 3 H Li 0 *r .4 .4* -48- Comp. No. R’ R 2
R
5
R
6 me phys. data 2.213 Ci Ci CH 3 H CH 3 H 1/2 Ca 2 0 2.214 C3- Ci CH 3 H CH 3 H NH(CH 3 )3 2.215 Cl Cl CH 3 H CH 3 H NH(C 2
H
5 OH) 3 i0 2.216 Cl CF 3 Gil 3 H CH 3 H NaG 2.217 Cl CF 3
ICH
3 H CH 3 H Li 0 2.218 Cl CF 3
CH
3 H Gi 3 H 1/2 Ca 2 0 2.219 Cl CF 3
CH
3 H CH 3 H NH(CH 3 3 0 2.220 Cl CF 3
CH
3 1 H CH 3 H NH(C 2
H
5
OH)
3 0 2 2.221 NO 2 H CH 3 H CH 3 H Na 2.222 NO 2 H Gil 3 i H CH 3 H Li 0 2.223 NO 2 H CH 3 H CH 3 H 1/2 Ca 2 2.224 NO 2 H CH 3 H CH 3 H NH(CH 3 3 2.225 NO 2 H ICH 3 H CH 3 H NH(C 2
H
5
OH)
3 0 2.226 H NO 2
CH
3 H ICH 3 H Na 2.227 H NO 2
CH
3 H CH 3 H Li@ 2.228 H NO 2
CH
3 H iCH 3 H 1/2 Ca 2 0 2.229 H NO 2 IcH 3 H iCH 3 H NH(CH 3 3 0 2.230 H NO 2
CH
3 H ICH 3 H NH(C 2 H50H) 3 2.231 H 1 H ICH 3 H ICH 3 H Na 2.232 H H CH 3 H CH 3 H Li 2.233 H H CH 3 H CH 3 H 1/2 Ca 2 2.234 H H lcH 3 H Gil 3 H NH(GH 3 3 Y- r- 2.23 .4 CC13. CH HC t H a 2 3 -l C C 1 C H H H H L i (D 2 0 4 2.23 .4 CC1 CH3 H 4 C3 H 1/2 Ca 2.240 Hl H1 CH 3 H Gil 3 H NH(C 2 H5OH) 3 0 2.236 Fl CF 3 Gil 3 H GH 3 H Na~ 2.242 Fl C1 3 Gi 3 H GH 3 H Li 0 2 2.23 C CFl 3 Gi 3 H Gil 3 H5 1/2 Ca 2.239 CF GC 3
GH
3 H CH 3 H NH(Cil 3 3 0 2.240 Cl Cd 3 Gil 3 H Gil 3 H NH(G 2
H
5 0H) 3 2.246 Fl CF Gil H Gil H Na 2.242 Fl F 3 Gil H Gil H Li 0 2.243 Fl GF 3 GH H Gil CN 1/2 Ga 2 0 2.244 Fl GF GH H Gil H NH(GH 3 3 2.2450 Fl F Gil H Gil H NH(C 2
H
5 0H) 3 2.246 Gi Gi3 H H H GN Na 0 2.247 Gi Gi3 H H H GN Li 0 2.248 Gi Gi3 H H H GN 1/2 Ga 2 0 2.24 Gi Gi H H H- GN NH(GH 3 3 0 2.255 Gi Gi3 H H H GN NH(C 2
H
5 0H) 3
E
0 2.251 G02 HF H H H GN Na r~ r -r A -II 0a 50 Comp. No. R 1
R
2 R5 phys. data 2.257 NO 2 H H H H CN Li 2.258 NO 2 H H H H CN 1/2 Ca 2 0 2.259 NO 2 H H H H CN NH(CH 3 3 2.260 NO 2 H H H H GN NH(C 2
H
5
OH)
3 2.261 H N02 H H H CN Na 2.261 H NO 2 H H H CN Li 2.263 H NO 2 H H H CN 1/2 Ca 2 2.264 H NO 2 H H H CN NH(CH 3 3
G
2.265 H NO 2 H H H CN NH(C 2 HsOH) 3 2.266 H H H H H CN Na 2.267 H H H H H CN Li 2.268 H H H H H CN 1/2 Ca 2 0 2.269 H H H H H CN NH(CH 3 3 2.270 H H H H H CN NH(C 2
H
5
OH)
3 2.271 Cl CC1 3 H H H CN Na 2.272 Cl CCil H H H CN Li® 2.273 Cl CC1 3 H H H CN 1/2 Ca 2 2.274 Cl CC1 3 H H H CN NH(CH 3 3 2.275 Cl CC1 3 H H H CN NH(C 2
H
5
OH)
3 2.276 F CF3 H H Hi CN Na 2.276 F CF 3 H H H CN Li 2.278 F CF 3 H H H CN 1/2 Ca 2 0 51~ S 0*9 ft~r o p” p 9* a -51- Comp. No. R’ R 2 phys. data 2.279 F CF 3 H H H ON NH(CH 3 3 0 2.280 F CF 3 H H H CN NH(C 2
H
5
OH)
3 0 2.281 Cl Cl H H H CN Na 2.282 Cl Cl H H H CN Li 2.283 Cl Cl B H H ON 1/2 Ca 20 2.284 Cl Cl H H H CN NH(CH 3 3 0 2.285 Cl Cl H H H ON NH(C 2
H
5 0H) 3 0 2.286 Cl CF 3 H H H CN Na 0 2.287 Cl CF 3 H H H ON Li 2.288 Cl CF 3 H H H ON 1/2 Ca 2 0 2.289 Cl CF 3 H H H CN NH(CH 3 3 0 2.290 Cl CF 3 H H H CN NH(C 2
H
5
OH)
3 2.291 NO 2 H OH 3 H H ON Na 2.292 NO 2 H CH 3 H H CN Li 2.293 NO 2 H OH 3 H H ON 1/2 Ca 2.294 NO 2 H OH 3 H H ON NH(CH 3 3 0 2.295 NO 2 H OH 3 H H CN NH(C 2
H
5 0H) 3 0 2.296 H Nz CH 3 H H CN Na 2.297 H NO 2
CH
3 H H ON Li 0 2.298 H NO, CH 3 H H ON 1/2 Ca 2 0 2.299 H NO 2
CH
3 H H ON NH(CH 3 3 0 2.300 H NO 2
CH
3 H H ON NH(O 2 HsOH) 3 0 Co p No 2 3: 40 64 ,tl0 R R R R’ R m 44s data No H’ R 3 H 5 H phys data50)3( 2.306 Hl H1 CH 3 H H CN Na G 2.302 H HC1 CH 3 H1 H CN Lio 0 2.303 Hl HC CH 3 H H CN 1/2 Ca 2 0 2.304 Hl HC1 Gil H H CN NH(C- 3 3
O
2.310 Hl H CH 3 H H CN. NH(C 2
H
5 0H) 3 2.311 F C1 3
CH
3 H H CN Na 2.307 Fi Cd 3
CH
3 H1 H CN Li 0 2.318 Fl CF 3 EH H CN 1/2 Ca 2.3094 F CI 3
CH
3 H H CN NH(C.H 3 3 2.315 Cl Cd 3
CH’
3 H H CN NH(C 2 HsOH) 3 2.3 1 Fl c CF 3 CH2 H H H Na® 2-317 Fl c CF 3 CH H H CN Li® 2.313 Fl CF 3 1-i-H2* H HN 1/2 Ca2( 2.314 Fl c CF 3
H
3 H CNH NH(CH 3 3 2.325 Fl CF CH 3 -F H H CN NH(C 2 H5OH) 3 2.321 Cl CF3 C 6
H
5
-CH
2 H H H Na®U 2.322 Cl CF 3
CH
5
-CH
2 H H H Na 53 Comp. No. R z R t e I phys. data 2,323 2.324 2.325 2.326 2.327 2.328 2.329 2.330 2.331 2.332 2.333 2.334 2.335 2.336 2.337 2.338 2.339 2. 34- 2.341 2.342 2.343 2.344 Cl Cl Cl
NO
2
NO
2
NO
2
NO
2
NO
2
H
H
H
H
CF
3
CF
3
CF
3
H
H
H
NO
2
NO
2
NO
2
NO
2
NO
2
H
H
H
CC1 3 CC1 3 CC’ 3
C
6
H
5
-CH
2
C
6 5
-CH
2 C6H 5 -CHi 2
C
6
H
5
-CH
2 CsHS-CH 2
C
6
H
5
-CH
2
C
6
H
5
-CH
2
C
6
H
5
-CH
2
C
6
H
5
-CH
2
C
6
H
5
-CH
2 CsH 5
-CH
2
C
6
H
5
-CH
2 C 6
H
5
-CH
2 Css -CH 2 C6HS-CH 2
C
6 lf 5
-CH
2 CrSHS-CH2-‘
C
6
H-
5
-CH
2 C6H 5
-CH
2
C
6 5
-CH
2
C
6 H5-CH 2 1/2 Ca 2 NH(CH3)3
NH(C
2
H
5 OH) 3 Na Li 1/2 Ca 2
NH(CH
3 3 NH(C2 HsOH)
ED
NaG Li 1/2 C
NH(CH
3 3
NH(C
2 H5OH)30 Na Li 0 1/2 Ca2D
NH(CH
3
NB(C
2
H
5 OH) 3 Na Li 0
E
1/2 Ca 2 NH(CH- 3 )3 3 -54- Comp. No. R 1 R 2 R R 4 R 5 RHM phys. data 2.345 Cl CC1 3
C
6
H
5
CH
2 H H H NH(C 2
H
5
OH)
3 0 2.346 F CF 3 C6H5-CH 2 H H )i Na 0 2.347 F CF 3
C
6 Hsl-CH 2 H H H Li 0 2.348 F CF 3
C
6
HS-CH
2 H H H 1/2 Ca 2 0 2.349 F CF 3 C6Hs-CH 2 H H H NH(CH 3 3 0 2.350 F CF 3 C6Hs-CH 2 H H H NHi(C 2 H5OH) 3 0 2.351 Cl CL C 6 H5 H H COaCH 3 Na 2.352 Cl Cl CsH 5 H H COOCH 3 Li 0 2.353 Cl Cl CFI H H COOCH 3 1/2 Ca 2 0 2.354 Cl Cl C6H 5 H H COOCH 3
NH(CH
3 3 0 2.355 Cl Cl C 6 H5 H H COOCH 3
NH(C
2
H
5
OH)
2 2.356 Cl CF 3 C0H 5 H H- COOCH 3 Na E 2.357 Cl CF 3
C
6 Hs H H COaCH 3 Li 0 2.358 Cl CF 3 C6s H H COOCH 3 1/2 Ca2G 2.359 Cl CF 3 C6H5 H H COOCH 3
NH(CH
3 3 0 2.360 Cl CF 3
C
6
H
5 H H COOCH 3
NH(C
2 H5OH)3 2.36 N02 H C65 H COOH3 0 2.362 NO 2 H C6H 5 H H COOCH 3
N
2.363 NO 2 H C 6
H
5 H H COOCH 3 1/2 Ca 2 2.364 NO 2 H C6H 5 H H COaCH 3
NH(CH
3 3 0 2.365 NO 2 H C 6 H5 H H COOCH 3
NH(C
2
H
5
OH)
3 0 0 0 0.0 Cp* a~ Comp. No. R’ R R 3
R
4 R5 R phys. data 2.366 H NO 2
C
6
H
5 H H COOCH 3 Na 2.367 H NO 2 615H H COOCH 3 Li? 2.368 H NO 2 C6H5 H H COOCH 3 1/2 Ca 2 2.369 H NO 2 C6H5 H H COOCH 3
NH(CH
3 3 0 2.370 H NO 2 CsH 5 H H COOCH 3
NH(C
2 HsOH) 3 2.37 H H C6H H H COOH~l a 0 2.371 H H C6H 5 H H COOCH 3 Na 2.37 H H CGH H H COOH3 12 C 2.372 H H C 6
H
5 H H COOCH 3 LiCH)3( 2.373 H H C 6
B
5 H H COOCH 3 1/(2B0) C D 2.374 Hl H1 C6H5 H H COOCH 3 NH (CH) 2.375 Hl HC3 CH H H COOCH 3 LHi 2
O)
3 2.376 Cl CC1 3
C
6
H
5 H H COOCH 3 Na a 2.379 Cl CC13 C 6
H
5 H H COOCH 3 Li 0 H)3( 2.3780 Cl CC1 3 C6s H H COOCH 3 1/(2H0) Ca 2 2.379 Cl Cd 3 C6H5 H H COOCH 3 NH (CH) 2.382 Cl CFl 3 CsH5 H H COOCH 3 NiH(C 2
H
3 2.381 F CF 3
C
6 H5 H H COOCH 3 Na 0 C 2 2.382 F CF 3
C
6
H
5 H H COOCH 3 Li 0 H33 2.385 F CF 3 C6H 5 H H KOO0CH 3
NH(C
2
H
5
OH)
3 0 -56 P.2.1. Preparation of the pyridinecarboxylic acid halides of formula II P.2.1.1. Preparation of 5-trifluoronethylpyridine-2-carboxylic acid chloride 9.8 ml (0.11 mol) of oxalyl chloride are added dropwise to a suspension of 22.9 g (0.1 mol) of the potassium salt of 2-carboxylic acid and 10 drops of DMF in 250 ml of toluene, the temperature rising to 40 0 C and brisk evolution of gas occurring. The whole is St then stirred for 2 hours at 40°C. The light-brown suspension is subsequently concentrated by evaporation on a rotary evaporator, stirred Swith 250 ml of absolute ether, filtered and concentrated by evaporation C t again.
17.8 g (85 of the title compound of formula
CF
3 N CO-Cl are isolated in the form of a brown oil (Compound No. 3.078).
S P.2.1.2. Preparation of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid ethyl ester 216 g (1 mol) of 2,3-dichloro-5-trifluoromethylpyridine, 16.7 g of [PdCl 2 (PPh 3 2 and 420 ml (3 mol) of triethylamine are stirred for 14 hours at t bar and 100 C in 3.3 1 of ethanol in a CO atmosphere. The whole is then concentrated by evaporation on a rotary evaporator at 40 0 C. The resulting mass is stirred with 2 1 of ether, the triethylamine hydrochloride is filtered off, and the filtrate is concentrated by evaporation on a rotary evaporator. 245 g of a brown oil are obtained, which is purified on silica gel with ethyl acetate/hexane 206.8 g of the title compound of formula
CF
3 Cl0 I I N \OOC 2
H
are isolated in the form of a yelUow oil (Compound No. 3.005).
I I
K.
57 P.2.1.3. Preparation of 3-chloro-5-trifluoromethylpyridine- 2 -carboxylic acid 76 g (0.3 mol) of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid ethyl ester are stirred for 6 hours with 165 ml (0.33 mol) of 2N NaOH.
The resulting solution is washed twice with methylene chloride. The aqueous solution is then adjusted to pH 1 with 37 hydrochloric acid and the product is filtered off with suction and dried at room temperature in vacuo.
0 0 00 65 g (96 of the title compound of formula 0. 0
SCF
3 C1 a o e I I o* .N
COOH
o o 0 o° are isolated in the form of white crystals having a melting point of 135 0 C (decomp.) (Compound No. 3.039).
P.2.1.4. Preparation of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid chloride o o* 16.9 g (75 mmol) of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid are suspended in 75 ml of hexane. After the addition of 2 drops of DMF 7 ml (80 mmol) of oxalyl chloride in 25 ml of hexane are added dropwise.
The whole is then stirred for 4 hours at 50 0 C until the evolution of gas has ceased. The reaction solution is filtered and concentrated by 0 evaporation on a rotary evaporator.
o 0 18 g (98 of the title compound of formula
CF
3
.C
F i I \cocl \COC1 are isolated in the form of a yellow oil (Compound No. 3.073).
The compounds of Table 3 can be synthesised analogously to the above preparation processes.
-58- P.2.1.5. Preparation of 3,5-dichloropyridine-2-carboxylic acid ethyl ester 250 g (1.3 mol) of 95 2,3,5-trichloropyridine are reacted and purified as described in P.2.1.2.
147 g (51.5 of the title compound of formula Cl Cl II I \N \CO-O–C2Hs S are isolated in the form of a yellow oil (Compound No. 3.139).
P.2.1.6. Preparation of 3-chloro-5-methylthio-2-carboxylic acid ethyl ester 8.6 g (0.18 mol) of methylmercaptan are introduced into a suspension of 17.9 g (0.16 mol) of potassium tert.-butoxide and 4.8 g of polyethylene glycol 1500 in 480 ml of toluene at from 25 to 30 0 C. The whole is then stirred for 15 minutes at 35 0 C. The resulting white suspension is cooled Sto -30 0 C and 35.2 g (0.16 mol) of 3,5-dichloropyridine-2-carboxylic acid ethyl ester are added, the whole is warmed to from 20 to 25 0 C and stirred t tt at that temperature for 15 hours. The potassium chloride is filtered off S from the reaction mixture and the filtrate is concentrated by evaporation on a rotary evaporator. 41 g of a yellow oil are obtained, which is purified on silica gel with petroleum ether/ether t4” S16 g (43.3 of the title compound of formula 6 C1 0-C2Hs are isolated in the form of a yellow oil (Compound No. 3.018).
P.2.1.7. Preparation of 3-chloro-5-methylthiopyridine-2-carboxylic acid 22 g (0.095 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid ethyl ester are reacted and purified analogously to P.2.1.3..
I
59 18.3 g (94.7 of the title compound of formula CH3-S /C \N \COOH are isolated in the form of white crystals (Compound No. 3.052).
P.2.1.8. Preparation of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride 9.8 g (0.048 mol) of 3 rloro-5-methylthiopyridine-2-carboxylic acid are suspended in 65 ml of hexane and 25 ml of dichloroethane. After the addition of 2 drops of DMF and heating to 55 0 C, 4.9 ml (0.055 mol) of ,oxalyl chloride are added dropwise. The whole is then stirred for 4 hours at 55°C, until the evolution of gas has ceased. The reaction solution is filtered and concentrated by evaporation on a rotary evaporator.
10.6 g (99.5 of the title compound of formula CH3S .Cl N CO-Cl O are isolated in the form of yellow, wax-like crystals (Compound No. 3.086).
P.2.2.1. 3-Chloro-5-methylsulfonyl-pyridin-2-carboxylic acid S ethylester 44 g (140 mmol) 55 3-chloroperbenzoic acid in 150 ml dichloromethane are added to a solution of 16.2 g (70 mmol) of din-2-carboxylic acid ethylester in such a manner that the temperature Sdoes not exced 30’C. The mixture is then stirred for 15 hours at room temperature and again 19 g (70 mmol) 3-chloroperbenzoic acid in 75 ml dichloromethane are added to this suspension to complete reaction. It is then stirred for another 3 hours at room temperature. The white suspension is diluted with 200 ml dichloromethane and filtered off from the 3-dichlorobenzoic acid. The filtrate is washed with 5 NaHC03 solution and water and concentrated by evaporation on a rotary evaporator.
S’
i_ i I~_ 60 15.3 g (83 of the title compound formula CH3-S02 Cl II I N COO-C 2 Hs are isolated in the form of crystals of a m.p. of 90-93 0
C
(Compound No. 3.017).
P.2.2.2. 3-Chloro-5-methylsulfonyl-pyridine-2-carboxylic acid 13.2 g (0.05 mol) 3-chloro-5-methylsulfonyl-pyr.line-2-carboxylic acid ethylester are added to a mixture of 55 ml (0.055 mol) IN NaOH and 5.5 ml S ethanol. The temperature rises to 32 0 C. It is stirred for 3 hours at room S temperature. This solution is then diluted with 150 ml of water, washed twice with dichloromethane and is then adjusted at a low pH by adding 37 HC1. The product is filtered off, washed with ice water and dried.
10.4 g (88.3 of the title compound of formula
CH
3 -S0 2 Cl J~r1 COOH are isolated in the form of crystals with a m.p. of >150 0 C (decomp.) (Compound No. 3.051).
P.2.2.3. 3-Chloro-5-methylsulfonyl-pyridin-2-carboxylic acid chloride 9.9 g (0.042 mol) of 3-chloro-5-methanesulfonyl-pyridine-2-carboxylic S acid in 100 ml toluene and 4.4 ml (0.06 mol) thionylchloride are heated up to the boiling point for 2 hours. The brovn suspension is then concentrated by evaporation on a rotary evaporator.
10.4 g (97.5 of the title compound of formula
CH
3
-SO
2 /.C1 COC1 are isolated in the form of a brown wax (Compound No. 3.086).
ls~~LW 61 Table 3 Compounds of formula /i ~N \C0-Y Comp. No.
3.001 3.002 3.003 3.004 3.005 3.006 3.007 3.008 3.009 3.010 3.011 3.012 3.013 3.014 3.015 3.016 3.017 3.018 3.019 3.020 3.021 3.022 3.023 3.024 3.025 3.026 3.027 3.028 3.029 3.030 3.031 3.032 3.033 3.034 3.035 3.036 3.037 3.038 3.039 3.040 3.041 3.042 3.043 3.044 R1 R2 y Cl Cl OC 2 Hs Cl H 0C 2 H5 H Cl OCZHs H H 0C 2 Cl CF’, OC 2 NO H OC 2 Hs H NO 2
OC
2 H5 N02 C1 0C 2
HS
CF
3 H 0C 2
H
5 H CF 3
OC
2 H5
OCH
3 H OC 2 Hs CN H C 2
H
OCH
3 Cl OC 2 CN C1 0C 2 Br Cl OC 2
H
5
SCH
3 Cl OC 2
H
5 SOZCH3 C1 C 2
H
5 Cl SCH 3
OC
2 H5 Cl S0CH3 OC 2 Cl S0 2 rH 3 0C 2
SOCH
3 Cl OC 2 Hs
SO
2 CH3 H OC 2 Hs H SO 2 CH3 OC 2
H
H CH3 C 2 Hs Cl F 0C 2
H
5 H CF 3
OC
2 Hs F F OC2H F CF 3 0C 2
H
CF3 F 0C 2
H
H CC13 0C 2
H
CC13 H OC 2
H
Cl CC13 0C 2
H
CC1 3 Cl OC 2 CH3 H OC 2 Hs Cl Cl
OH
cl H
OH
H Cl
OH
H H
OH
Cl CF3
OH
N02 H
OH
H N02
OH
N02 Cl
OH
CF3 11 OH H CF 3
OH
phys. data oil oil m.p.
m.p.
m.p.
m.p.
oil 56-58 0
C
:9-91 0
C
43-45 0
C
77-80 0 0 90-930C I1 oil oil m.p.
m.p.
m.p.
157 0
C
)125 0
C
135 0
C
(deconp.) (decomp.) (decomp.) m.p. 135 0 C (decomp.) m.P. 129-131 0
C
r 62 Comp. No.
3.045 3.046 3.047 3.048 3.049 3.050 3.051 3.052 3.053 3.054 3.055 1 3.056 r 3.057 r 3.058 3.059 3.060 t4 3.061 S 3.062 S 3.063 3.064 3.065 3.066 3.067 3.068 S 3. 069 3.070 3.071 ~3.072 3.073 4 3.074 3.075 3.076 3.077 t 9f 3.078 444 3.079 4 1 3.080 ‘~3.081 3.082 3.083 3.084 3,.-08 5 3.086 3.087 3.088 3.089 3.090 3.091 3.092 3.093 3.094 OCH 3
CN
OCH
3
CN
Br S CH 3
SO
2
CH
3 Cl Cl
SOCH-
3
SO
2
CH
3
H
H
Cl
F
F
CF
3
H
CC1 3
CH
3 Cl
H
H
Cl
NO
2
H
NO
2
CF
3
H
OCH 3
CN
OCH 3
CN
S CH 3 SO2 CH 3 Cl Cl Cl
SOCH
3 S02 CH 3
H
H
Cl
H
R2
H
Cl Cl Cl Cl Cl1
CH
SOCH
3
SOCH
3 S0C Hl
SH
3 S0CH 3
FH
F
F
F
3
F
CC’
Hc
CCH
CUl Hl
CH
Hl Cl Hl
CF
HF
NO
N0l Hl
CF
HF
H
H
Ca Cl Cl Cl
SCH
3
SOCH
3 S 02 CI1 Cl
H
SO
2
CH
3
CH
3
F
CF
3
Y
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
Cl1 Cl Cl1 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl1 Cl r l phys. data m-P. >150’C (decomp.) solid m-p. >135’C (decomp.) m-p. >143’C (decomp.) m-p. 54-56’C so lid solid oil oil oil solid oil oil 63 Comp. No. I R’ R 2 y I !phys. data 3.095 3.096 3.097 3.098 3.099 3.100 3.101 3.102 3.103 3.104 3.105 3.106 3.107 3.108 3.109 3.110 3.111 3.112 3.113 3.114 3.115 3.116 3.117 3.118 3.119 00 3.120 3.121 3.122 3.123 3.124 3.125 3.126 3.127 3.128 3.129 3.130 3.131 3.132 3.133 3.134 3.135 3.136 3.137 3.138 3.139
F
F
CF
3
H
CC13 Cl CC1 3
CH
3 Cl Cl Cl
H
H
H
H
H
H
H
H
H
H
Cl C1 C1 C1 C1 C1 c1 C1 Cl Cl Cl Cl C1 Cl Cl Cl Cl Cl
SCH
3 Cl Cl Cl Cl Cl
F
CF
3
F
cc13
H
CC1 3 Cl
H
OCH
3
OCH
3
OCH
3
OCH
3
OCH
3
OCH
3 0C 3
H
7 i) 0C 3
H
7 (i) 0C 3
H
7 (i
OCH
3
SCH
3
SCH
3
SCH
3 SC2H5
SC
2 H5
SC
2 H5 SOC2H5 SOC2H5
SOC
2
HS
S0 2
C
3
H
7 (i)
SOC
3 H7(i)
SC
3
H
7 (i)
SO
2
C
3 H7(i)
SOC
3
H
7 (i)
SC
3
H
7 (i) S0 2
C
3
H
7 (i)
SOC
3
H
7 (i)
SC
3 H7(i)
OC
3 H.(i) 0C 3
H
7 (i) 0C 3
H
7 (i)
SCH
3 Br Br Br
OCH
3 Cl Cl Cl Cl Cl Cl Cl Cl Cl
OC
2
HS
OH
Cl
OC
2 Hs
OH
Cl
OC
2
OH
Cl
OCH
3 0C 2
H
5
OH
Cl
OH
OC2Hs Cl
OH
0C 2
H
Cl
OH
OH
OH
0C 2
H
OC
2
HS
OC
2
H
cl Cl Cl
OH
0C 2
H
Cl
OC
2 Hs
OH
OC
2
H
Cl
OCH
3 COOc 2
H
5 solid solid m.p. 27-74 0
C
m.p. 46-48 0 c m.p. 159-160 0
C
solid m.p. 60-70 0
C
m.P.
oil 72-74 0 c 64 F. Formulation Examples Example Fl: Formulation Examples for active ingredients of formula I (throughout, percentages are by weight) a) Emulsifiable concentrates a compound according to Table 1 or 2 calcium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of ethylene oxide) tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) cyclohexanone xylene mixture Emulsions of any desired concentration concentrates by dilution with water.
b) Solutions a compound according Table 1 or 2 ethylene glycol monomethyl ether polyethylene glycol MW 400 N-methyl-2-pyrrolidone epoxidised coconut oil a) 20 5% b) 40 8% c) 50 5.8 12 15 70 25 4.2 20 20 can be produced from such a) b) 80 10 20 S 70 20 c) 90 These solutions are suitable for application in the form of micro-drops.
c) Granulates a compound according to Table 1 or 2 kaolin highly dispersed silicic acid attapulgite a) 5% 94 1 b) 10 90 The active ingredient is dissolved, sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
d) Dusts a) b) c) a compound according to Table 1 or 2 2 5 8 highly dispersed silicic acid 1 5 5 talcum 97 10 kaolin 90 77 Ready-for-use dusts are obtained by homogeneously mixing the carriers with the active ingredient.
e) Wettable powders a) b) a compound according Table 1 or 2 20 60 sodium lignosuifonate 5 5 sodium lauryl sulfate 3 6 octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) 2 highly dispersed silicic acid 5 27 kaolin 67 S The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
f) Extruder granulate a compound according to Table 1 or 2 10 S sodium lignosulfonate 2 carboxymethylcellulose 1 kaolin 87 The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
g) Coated granulate a compound according to Table 1 or 2 3 polyethylene glycol (MW 200) 3 kaolin 94 u !l 66- The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
h) Suspension concentrate a compound according to Taule 1 or 2 40 ethylene glycol 10 nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 sodium lignosulfonate 10 carboxymethylcellulose 1 S 37 aqueous formaldehyde solution 0.2 silicone oil in the form of a 75 aqueous emulsion 0.8 water 32 The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be produced by dilution with water.
t B. Biological Examples i Example Bl: Pre-emergence herbicidal action t In a greenhouse, immediately after sowing the test plants in seed trays the surface of the soil is treated with an aqueous dispersion of the test compound obtained from a 25 emulsifiable concentrate. Various rates of application of active ingredient/hectare are tested. The seed trays are kept in the greenhouse at 22-25 0 C and 50-70 relative humidity and the test is evaluated after 3 weeks.
The herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1 total damage of the test plants, 9 no herbicidal actic, on the test plants).
~I_
67 Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in the case of crop plants). The test results for compound No. 1.005 are compiled in Table 4.
Table 4 Rate 2000 1000 of application [g/ha] 5000 250 125 Test plant barley wheat maize sorghum Abutilon Chenopodium Sp.
t Solanum nigrum Veronica Sp.
7 7 8 9 8 9 9 9 9 2 2 2 1 1 1 1 1 2 1 1 4 Example B2: Post-emergence herbicidal action A number of weeds, both monocotyledons and dicotyledons, are sprayed after emergence (at the 4- to 6-leaf stage) with an aqueous dispersion of active ingredient at a rate of 250 g to 2 kg of active ingredient per hectare and kept at 24-26°C and 45-60 relative humidity. 15 days after the treatment the test is evaluated in accordance with the evaluation ao t scheme described in Example B1.
The test results for compound 1.005 are compiled in Table a..
c0 cl
L
ct
I
L~Ur -68- Table rate of application [g/ha] Test plant 2000 1000 5000 250 barley 9 9 9 9 wheat 8 9 9 9 maize 8 9 9 9 sorghum 7 8 9 9 rice (dry) 7 8 9 9 Abutilon 1 1 2 3 Chenopodium Sp. 1 1 1 2 Solanum nigrum 1 1 1 2 Sinapis 2 2 3 3 Example B3: Herbicidal action in paddy The water weeds Echinochloa crus galli and Monocharia vag. are sown in plastics beakers (60 cm 2 surface area, 500 ml volume). After sowing, the beakers are filled to the soil surface with water. 3 days after sowing, the water level is raised to slightly above (3-5 mm) the surface of the soil. Application is carried out 3 days after sowing by spraying an aqueous emulsion of the test substances onto the vessels at a rate of Sapplication of 60 to 250 g of active ingredient per hectare. The plant beakers are then placed in a greenhouse under optimum growth conditions for the rice weeds, i.e. at 25 0 -30 0 C and high humidity. The tests are evaluated 3 weeks after the application. The compounds of Table 1 damage the weeds but not the rice.
n

Claims (15)

1. Cycloexane-l,3-diones of formula I or V’ R3 N R4~ 0~ \RS or R 3 \iN1 RS 5 ft ft 5 4511 St #9 5 If 5 9 II

9. .4 9 *1$t I I 4 Si a t U cc 41 I S 555 4. a a. in which R’ and R 2 independently of one another are each hydrogen; halogen; nitro; cyano; Cl-Cialkyl; Cl-C 4 alkoxy; C1-C 4 alkyl-S(O) COR 8 Gl-C4haloalkoxy; Or Cl-Ci~haloalkyl; R 3 R4 and R5 independently of one another are each hydrogen; Cl-Ct~alkyl; or phenyl or benzyl each unsub- stituted or substituted by up to three identical or different substi- tu’-nts from halogen, nitro, cyano, Cl-C 4 alkyl, Ci-C 4 alkoxy, CI-C4- alkyl-S(O) C 1 -C~haloalkyl, Cl-C4haloalkyl-S(O) n- and Cl-C4haloalkoxy; R 6 is hydrogen; Cl-C~.alkyl; Cl-C~alkoxycarbonyl; or cyano; R 7 is OH; or M;R 8 is OH; C 1 -Ci~alkoxy; NH 2 C-Cz~alkylamino; or di-Cl-~lyaio n is 0, 1 or 2; HP is a cation equivalent of a metal ion or of an ammonium ion that is unsubstituted or substituted by up to three C1-C 4 alkyl, G1-C4hydroxyalkyl or Ca-Calkoxy-C1-C+alky1 groups. 2. Cyclohexanediones according to claim 1 of formula I or V’ R5 \R6 172 o r R 3 N R 4/ \R7 R 5 \R6 I t 3. Cyclohexanediones according to claim 1 of formula I or I R4 0 I or R R4 \R7 R tir 70 Cyclohexanedione according to claims 2 and 3 of formula I or 1 7 R’ \R 6 or Ln which the radicals R 1 and R 2 are bonded in the 3- and 5-positions of :he pyridine ring and the pyridinecarbonyl system is bonded by way of :he 2-position of the pyridine ring. Cyclohexanediones according to claim 1 of formula I or V’ 7 R4~ O R 5 /”R r” \N R~~R :4*in which RI is hydrogen; halogen; nitro; cyano; Ca-C 4 alkyl; C 1 -CL~alkoxy; Ca-Ci~alkyl-S(O) -;CaR 8 Cl-Cz~haloalkoxy; or Ca-Ci 4 haloalkyl; R 2 is n hydrogen; halogen; nitro; cyano; C 1 -C~alkyl; Ci-Ci~alkoxy; C 1 -Ci~halo- alkoxy; C 1 -Ct~alkyl-S(0) -;or Ca-C~haloalkyl; RI R4 and R 5 independently ofone another are each hydrogen; CI-Ci~alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, Cl-Ci~alkyl, CI-C~alkoxy, CI-Ci~alkyl-S(0) C 1 -‘Cihaloalkyl, Cl-C~haloalkyl-S(O) n- and Cl-Ci 4 halo- .:alkoxy; RI is hydrogen; CI-C~alkoxycarbonyl; or cyano; R 7 is OH; or 0 M R’ is OH; Cl-C~alkoxy; NH 2 G 1 -C~alkylamino; or di-C 1 -C~alkylamino; n is 0, 1 or 2; M is a cation equivalent of an alkali metal ion, an alkaline earth metal ion or an ammonium ion; of a mono -C 1 -C 4 -alkylammonium ion; of a di-Cl-Ci 4 -alkylammonium ion; of a tri-Ca-C 4 alkylammonium ion; or of a triethanolammonium ion. 6. Cyclohexanediones of formula I or V’ in which at least one of the radicals RI to RI is hydrogen, according to one or more of claims 1 to i: 71 7. Cyclohexanediones of formula I or I’ in which at least two of the radicals R 3 to R 6 are hydrogen, according to one or more of claims 1 to 8. Cyclohexanediones of formula I or I’ in which R 6 is cyano and R 5 is hydrogen, according to one or more of claims 1 to 9. Cyclohexanediones of formula I or I’ in which R 6 is cyano, R 5 is hydrogen and R 3 and R 4 independently of one another are each hydrogen or Ci-C4alkyl, according to one or more of claims 1 to 1 0. Cyclohexanediones of formula I or I’ in which R 6 is Ci-C4alkoxy- carbonyl, according to one or more of claims 1 to If

11. Cyclohexanediones of formula I or I’ in which R 7 is OH, according to one or more of claims 1 to

12. Cyclohexanediones of formula I or I’ in which R 7 is e0-M according to one or more of claims 1 to 4* It S13. Cyclohexanediones of formula I or I’ in which RI is hydrogen, 1t S chlorine, fluorine, nitro, trifluoromethyl, methoxy, bromine, methylthio, methylsulfonyl, carboxy, trichloromethyl or methyl, according to one or more of claims 1 to

14. Cyclohexanediones of formula I or I’ in which R 2 is hydrogen, chlorine, nitro, methylthio, methylsu2finyl, methylsulfonyl, methyl, fluorine, tzifluorcmethyl or trichloromethyl, according to one or more of claims 1 to Cyclohexanediones of formula I or I’ in which R I is hydrogen; fluorine; chlorine; bromine; nitro; cyano; methyl; trifluoromethyl; trichloromethyl; methoxy; methylthio; methylsulfinyl; methylsulfonyl; carboxy; carbamoyl; methoxycarbonyl; or ethoxycarbonyl; R 2 is hydrogen; fluorine; chlorine; nitro; trifluoromethyl; trichloromethyl; methylthio; methylsulfinyl; or methylsulfonyl; R 3 is hydrogen; Ci-C 3 alkyl; phenyl; -72 benzyl; or chlorophnnyl; R’ is hydrogen; or methyl-, R’ is hydrogen; or methyl; RI is hydrogen; cyano; methyl; or C 1 -C 2 alkoxycarbonyl; R 7 is OH; or 0 -t M+ is a cation equivalent of a sodium, lithium, calcium, t rime thylanmonium or triethanolammoniumn ion, according to any one of 16 t-ho5 as a rompoundof frmun–la r nyl)-cyclohex-l-en- 1-ol–3-one or 3-chloro-5-methylsulfonylpyridi.i–2-ylcarbonyl)-cyclo-

17. A process for the preparation of cyclohexanediones of formula I or V’ in which the radicals RI to R’ are as defined in any one of claims 1 to 11 or 13 to 16 and k’ is OH, which comprises a) reacting a cyclohexanedione of formula II, in which the radicals R 3 t are as defined hereinbefore, with a pyridine of formula III, in which RI and R 2 are as defined hereinbefore and X is halogen, preferably chlorine or bromine, or the radical R 1 OLRor -R 2 and R’ is C 1 -Ci 4 alkyl, phenyl or benzyl, in N1 the presence of a base P R 1 Y X_ base R’ R R5/ \R6 Ii III Ia (R 7 OH) ~-W+-R2 or R i- rl’ \1 Ia’ (R 7 OH) 73 b) thermally rearranging an ester of formula IV or IV’ in which the radicals RI to R 6 are as defined hereinbefore Q N; R3~R IV or A ~R’ R4/ 0 R5 \R 6 Ta (R 7 =OH) or Ia’ .R 7 OHj) C tr t. 41 1 I I 44I~ 4 I I. 4: I *1 I II It I CII 4* q R Ri R4/ 2 \R 6 IV I

18. A process for the preparation of salts of the cyclohexanediones of formula I or I’ in which the radicals R1 to R6 and M are as defined in any one of claims 1 to 10 or 12 to 15 and k 7 is 0 M which comprises reacting a cyclohexanedione Ia or la’ in which R 1 to R 6 are as defined hereinbefore and R 7 is OH with a base V in which B is OHGH MO being as defined hereinbefore 74 aR 2 Ia (R 7 OH) B 4 R 3 1 2 -R 2 R 3- R 5 \R 6 I -7 o- 2 R/ 3 R3 R 7 o 6 la’ (R 7 OH) 4 4 44 C #4 o 44 4 *444 44 44 49 *9 4 49 44 4* 4 4 4 #44444 o 4 44,4 o #4 9 44 4, 4 44 9 444 4 4 4444 44 4 4 44 44 4 44 4 *4 444444 4 4

19. A process for the preparation of compounds of formulas Ic or Ic’, in which one or more of the radicals R’ to R 6 is (are) C 1 -C 4 alkyl-S(O) n representing 1 or 2, and the remaining radicals are as defined in formula I or I’ in claim 1, which process comprises oxidizing a thioether of formula Id or Id’, wherein the radical from the group R 1 to R 6 that is to be oxidized is C -C 4 alkyl-S(O)n with n representing 0, and the remaining radicals are as defined in formula I or I’ in claim 1 X R R 4 0 RS \R6 Id (thioether, n representing 0) +-R 2 Rs SR’R6 R I R’ R6 oxidation Ic (sulfinyl or sulfonyl compound, n represent- ing 1 or 2) /Rl c t” R s1R R 3 R s 4 R NE 36f Id’ (thioether, n representing 0) Ic’ (sulfinyl or sulfonyl compound, n represent- ing 1 or 2) i 1. l ra~- 75 A herbicidal composition for controlling undesired plant growth containing a compound of formula I according to any one of claims 1 to 16 together with further adjuvants and/or carriers.

21. A process for the preparation of a herbicidal composition according to claim 20 which comprises mixing a compound of formula I with the adjuvants and/or carriers.

22. A method of controlling undesired plant growth at a locus, which method comprises treating the locus with a compound of formula I according to any one of claims 1 to 16 or a herbicidal composition according to claim 20 in a amount which effectively controls the undesired plant growth.

23. A method according to claim 22 for controlling weeds or grasses i in crops of useful plants. S, 24. method according to claim 23 for the pre- or post-emergence control of weeds or grasses in cereals, cotton, soybeans, maize, rice, sugar I 15 cane or sorghum. Seeds when treated with a herbicidally effective amount of a compound of formula I according to any one of claims 1 to 16 or a composition according to claim

26. A pyridinylcarbonylcyclohexenone derivative substantially as 20 herein described with reference to any one of Tables 1 to 3.

27. A process for preparing a pyridinylcarbonylcyclohexenone 8 o S* derivative, substantially as herein described with reference to any one of the Preparation Examples. ‘t 28. A herbicidal composition for controlling undesired plant growth containing a compound of claim 26 together with further adjuvants and/or carriers.

29. A herbicidal composition for controlling undesired plant growth, substantially as herein described with reference to the any one of the Formulation Examples.

30. A method of controlling undesired plant growth at a locus, which method comprises treating the locus with a compound of claim 26 or a composition of claim 28 or 29 in an amount which effectively controls the undesired plant growth. Seeds when treated with a herbicidally effective amount of a compound of claim 26 or a composition of claim 28 or 29. DATED this SIXTEENTH day of DECEMBER 1991 PLI Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON 336f

AU38929/89A
1988-07-25
1989-07-24
Pyridinyl carbonyl cyclohexenone derivatives

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1989-07-24
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IP Right Cessation

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AU38929/89A
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1989-07-25
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